Polymer-based resin compositions derived from cellulose and articles made using these compositions

ABSTRACT

An injection molded article comprising a thin-walled body portion formed from a polymer-based resin derived from cellulose, wherein the thin-walled body portion comprises:
         i. a gate position;   ii. a last fill position;   iii. a flow length to wall thickness ratio greater than or equal to 100, wherein the flow length is measured from the gate position to the last fill position; and   iv. a wall thickness less than or equal to about 2 mm; and   wherein the polymer-based resin has an HDT or at least 95° C., a bio-derived content of at least 20 wt %, and a spiral flow length of at least 3.0 cm, when the polymer-based resin is molded with a spiral flow mold with the conditions of a barrel temperature of 238° C., a melt temperature of 246° C., a molding pressure of 13.8 MPa, a mold thickness of 0.8 mm, and a mold width of 12.7 mm.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a national stage filing under 35 USC § 371 ofInternational Application Number PCT/US2017/060823, filed on Nov. 9,2017, which claims the benefit of the filing date to U.S. ProvisionalApplication Nos. 62/420,989 filed on Nov. 11, 2016, 62/505,261 filed onMay 12, 2017, 62/505,268 filed on May 12, 2017 and 62/513,467 filed onJun. 1, 2017 the entire disclosures of which are incorporated byreference herein.

FIELD OF THE INVENTION

This invention belongs to the field of polymer-based resins derived fromcellulose, and particularly to cellulose esters useful for relativelyhigh temperature applications. Plastic articles made using thesecompositions, such as eyeglass frames, automotive parts, housings, andtoys are also provided.

BACKGROUND OF THE INVENTION

There has been increasing interest in materials produced frombio-sources such as wood, cotton or corn. Wood is a preferred sourceover corn as it does not potentially compete with the bio-based resin'suse as a food source. In addition, common materials produced from corn,e.g., polylactic acid (PLA), have limitations on physical propertiesthat restrict the range of applications for which they can be used.

It would be beneficial to have a bio-based material that has physicalproperties that can compete with engineering plastics, such aspolycarbonate, nylon or ABS, in a range of applications. Celluloseacetate compositions have been used for molded articles, but typicallyhave a heat deflection temperature (HDT) of less than 90° C.Commercially available cellulose esters that are utilized in meltprocessing and forming of articles typically contain significant amountsof plasticizer to allow for processing and to impart toughness to themolded article. However, the addition of plasticizer has drawbacks, asit will decrease the HDT relative to the base cellulose ester and limitthe use of the cellulose ester materials for applications that canaccommodate an HDT below about 90° C. Also, cellulose ester moldedarticles can experience plasticizer exudation during use.

It would be beneficial to be able to provide polymer-based resinsderived from cellulose that can be melt processed and articles made fromsuch compositions that do not have such drawbacks.

SUMMARY OF THE INVENTION

Surprisingly, it had been discovered that compositions of celluloseesters can be prepared having significant bio-based content and HDTsexceeding 90° C., or 95° C. In embodiments of the invention, this can beachieved by reducing the amount of plasticizer, and in certainembodiments eliminating the use of plasticizer, in the compositions,while maintaining a good balance of physical properties and the abilityto process the compositions in conventional molding operations. Theelimination of the plasticizer can eliminate the problems associatedwith plasticizer exudation during use.

It has been discovered that shaped articles can be prepared frombio-based plastic materials that have properties similar with or betterthan molded articles produced from oil-based engineering thermoplastics.More specifically, these shaped articles are produced from bio-basedplastic material with a heat distortion temperature (HDT) greater than90° C., or greater than 95° C. This elevated HDT vastly improves theability of these articles to experience high temperature environments(i.e. dishwashing, holding hot liquids, sun exposure, etc.), resistcreep and warpage during hot warehouse storage or during use inapplications under moderate load or stress, and prevent loss indimensional stability during use.

These bio-based plastic materials can process better into moldedarticles than other engineering thermoplastics, and the shaped articlescan have higher stiffness than articles made from other materials, havesuperior toughness to articles produced from other bio-plastics, andhave superior stress crack resistance to articles produced from otherengineering thermoplastics.

In one aspect of the invention, it is directed to a shaped articlecomprising a polymer-based resin derived from cellulose, wherein thepolymer-based resin has an HDT or at least 90° C., or at least 95° C., abio-derived content of at least 20 wt %, and has at least one of thefollowing properties chosen from: flexural modulus of greater than 1900MPa as measured according to ASTM D790 using a 3.2 mm thick bar hat hasbeen subjected to 50% relative humidity for 48 hours at 23° C.; anotched izod impact strength of greater than 80 J/m as measuredaccording to ASTM D256 using a 3.2 mm thick bar that has been subjectedto 50% relative humidity for 48 hours at 23° C.; a spiral flow length orat least 3.0 cm, when the polymer-based resin is molded with a spiralflow mold with the conditions of a barrel temperature of 238° C., a melttemperature of 246° C., a molding pressure of 13.8 MPa, a mold thicknessof 0.8 mm, and a mold width of 12.7 mm; a flex creep deflection of lessthan 12 mm, measured using a molded bar having dimensions of 5″ length,0.5″ width, and 0.125″ thickness positioned horizontally on a fixturewith a 4″ span, inside a dry oven for 68 hours at 90° C. with a nominal500 psi stress on the center of the span; a transmission of at least 70%measured according to ASTM D1003 using a 3.2 mm plaque after injectionmolding at a barrel set point of 249° C. and a residence time of 5 min;a ΔE value of less than 25, using a 3.2 mm plaque after injectionmolding with a barrel temperature of 249° C. and a residence time of 5min; or an L* color of at least 85, measured according to ASTM E1348using a 3.2 mm plaque after injection molding with a barrel temperatureof 249° C. and a residence time of 5 min. In embodiments, thepolymer-based resin has at least 2, or at least 3 of the listedproperties. In certain embodiments, the polymer-based resin containsplasticizer in an amount from 1 to 15 wt %, or from 1 to 10 wt %, orfrom 1 to 9 wt %, or none. In certain embodiments, the polymer-basedresin contains less than 5 wt %, or less than 4 wt %, or less than 3 wt%, or less than 2 wt %, or less than 1 wt %, or has no addedplasticizer.

In embodiments of the invention, the shaped articles can be chosen frominjection molded articles, extrusion molded articles, rotational moldedarticles, compression molded articles, blow molded articles, injectionblow molded articles, injection stretch blow molded articles, extrusionblow molded articles, sheet or film extrusion articles, profileextrusion articles, gas assist molding articles, structural foam moldedarticles, or thermoformed articles.

In embodiments of the invention, the shaped article is chosen fromopaque articles, transparent articles, see-through articles, thin-walledarticles, technical articles (e.g., articles having a complex design),articles having high design specifications, intricate design articles,articles made from molds that are difficult to fill under typicalmolding operations or conditions, wearable articles, body contactarticles, containers (including containers for materials intended forbody contact), food contact articles, household articles, generalconsumer products, packaging articles, medical articles, or componentsthereof.

In embodiments, the transparent or see-through articles can be chosenfrom electronic displays, electronic display lenses or windows,electronic display covers, ophthalmic devices, ophthalmic lenses,ophthalmic frames, sunglasses, sunglass lenses, automotive interiorparts, lighting devices, LED lights, lighting covers, headlight coversor enclosures, appliance parts, sporting goods, vehicle parts,instrumentation parts, instrumentation covers, timekeeping device parts,personal devices, personal electronic devices, medical devices, personalprotection devices, safety devices, tools, guards, office supplydevices, kitchen devices, kitchen articles, cutlery, glassware, barware,artist supply devices, decorative items, packaging, or componentsthereof.

In embodiments, the thin-walled articles can be chosen from foodpackaging articles (e.g., food containers and lids), automotive or othertransportation articles (e.g. both structural and non-structural carparts), mobile telecommunications or handheld electronic articles (e.g.mobile phone housings), medical articles (e.g. syringes and connectors),computing equipment articles (e.g. computer housings), electronicdevices, electronic parts, business machine housings, electronichousings, optical or electrical connectors, electronic covers, screensof electronic devices, touch screens, covers for screens or touchscreens, or components thereof.

In embodiments, the technical articles, articles having high designspecifications, intricate design articles, and difficult to moldarticles can be chosen from transportation or automotive parts,electrical/electronic equipment parts, perfume or cosmetic containers,ophthalmic articles, lighting devices, timekeeping devices, medicaldevices, or components thereof.

In embodiments, the wearable articles or body contact articles can bechosen from eyeglass frames, eyeglass lenses, sunglass frames, sunglasslenses, goggles, wearable electronics, headphones, ear buds, watches,personal devices, personal electronics devices, medical devices,personal protection devices, safety devices, jewelry, water sportarticles, or components thereof.

In embodiments, the household articles or general consumer articles canbe chosen from kitchenware, barware, outdoor furniture, indoorfurniture, furniture components, shelves, shelving dividers, slat walls,toys, luggage, appliances, small appliances, storage containers, officesupply items, bathroom devices or fixtures, tools, home electronics, orcomponents thereof.

In embodiments, the packaging articles can be chosen from packagingsystems, product packaging, rigid medical packaging, containers,thin-walled cups, beakers, buckets, pails, folding boxes, crates, orcomponents thereof.

In embodiments, the medical articles or devices can be chosen fromdisposable items, syringes, tubing, instruments, instrumentation,handles, medical packaging, medical containers, housings, or componentsthereof.

In another aspect, the invention is directed to an injection moldedarticle comprising a thin-walled body portion formed from apolymer-based resin derived from cellulose, wherein the thin-walled bodyportion comprises:

-   -   i. a gate position;    -   ii. a last fill position;    -   iii. a flow length to wall thickness ratio greater than or equal        to 100, wherein the flow length is measured from the gate        position to the last fill position; and    -   iv. a wall thickness less than or equal to about 2 mm; and

wherein the polymer-based resin has an HDT or at least 90° C., or atleast 95° C., a bio-derived content of at least 20 wt %, or at least 40wt %, and a spiral flow length of at least 3.0 cm, when thepolymer-based resin is molded with a spiral flow mold with theconditions of a barrel temperature of 238° C., a melt temperature of246° C., a molding pressure of 13.8 MPa, a mold thickness of 0.8 mm, anda mold width of 12.7 mm. In embodiments, the polymer-based resin has aspiral flow length of at least 4.0, or at least 5.0 cm.

In one embodiment of the injection molded article, the polymer-basedresin further comprises at least one property chosen from: flexuralmodulus of greater than 1900 MPa as measured according to ASTM D790using a 3.2 mm thick bar hat has been subjected to 50% relative humidityfor 48 hours at 23° C.; a notched izod impact strength of greater than80 J/m as measured according to ASTM D256 using a 3.2 mm thick bar hathas been subjected to 50% relative humidity for 48 hours at 23° C.; aflex creep deflection of less than 12 mm, measured using a molded barhaving dimensions of 5″ length, 0.5″ width, and 0.125″ thicknesspositioned horizontally on a fixture with a 4″ span, inside a dry ovenfor 68 hours at 90° C. with a nominal 500 psi stress on the center ofthe span; a transmission of at least 70 measured according to ASTM D1003using a 3.2 mm plaque after injection molding at a barrel set point of249° C. and a residence time of 5 min; a LE value of less than 25, usinga 3.2 mm plaque after injection molding with a barrel temperature of249° C. and a residence time of 5 min; or an L* color of at least 85,measured according to ASTM E1348 using a 3.2 mm plaque after injectionmolding with a barrel temperature of 249° C. and a residence time of 5min. In embodiments, the polymer-based resin comprises at least 2, or atleast 3 of the listed properties. In embodiments, the polymer-basedresin contains less than 5 wt %, or less than 4 wt %, or less than 3 wt%, or less than 2 wt %, or less than 1 wt %, or has no addedplasticizer.

In embodiments, the gate position comprises a gate having a gate size,wherein the ratio of gate size to wall thickness is 1:1 or less, or0.5:1 or less. In embodiments, the gate size is 1.0 mm or less, or 0.5mm or less. In embodiments, the wall thickness is 1.5 mm or less, or 1.0mm or less, or 0.5 mm or less.

In another aspect of the invention, it is directed to a housingcomprising a polymer-based resin derived from cellulose, wherein thepolymer-based resin has an HDT or at least 90° C., or at least 95° C., abio-derived content of at least 20 wt %, and has at least one of thefollowing properties chosen from: flexural modulus of greater than 1900MPa as measured according to ASTM D790 using a 3.2 mm thick bar hat hasbeen subjected to 50% relative humidity for 48 hours at 23° C.; anotched izod impact strength of greater than 80 J/m as measuredaccording to ASTM D256 using a 3.2 mm thick bar hat has been subjectedto 50% relative humidity for 48 hours at 23° C.; a spiral flow length orat least 3.0 cm, when the polymer-based resin is molded with a spiralflow mold with the conditions of a barrel temperature of 238° C., a melttemperature of 246° C., a molding pressure of 13.8 MPa, a mold thicknessof 0.8 mm, and a mold width of 12.7 mm; a flex creep deflection of lessthan 12 mm, measured using a molded bar having dimensions of 5″ length,0.5″ width, and 0.125″ thickness positioned horizontally on a fixturewith a 4″ span, inside a dry oven for 68 hours at 90° C. with a nominal500 psi stress on the center of the span; a transmission of at least 70measured according to ASTM D1003 using a 3.2 mm plaque after injectionmolding at a barrel set point of 249° C. and a residence time of 5 min;a ΔE value of less than 25, using a 3.2 mm plaque after injectionmolding with a barrel temperature of 249° C. and a residence time of 5min; or an L* color of at least 85, measured according to ASTM E1348using a 3.2 mm plaque after injection molding with a barrel temperatureof 249° C. and a residence time of 5 min. In embodiments, thepolymer-based resin at least 2, or at least 3 of the listed properties.In embodiments, the polymer-based resin contains less than 5 wt %, orless than 4 wt %, or less than 3 wt %, or less than 2 wt %, or less than1 wt %, or has no added plasticizer. In one embodiment, the housing isan electronic housing.

In embodiments in accordance with the various aspects of the inventiondisclosed herein, the polymer-based resin comprises a cellulose ester.In certain embodiments, the cellulose ester is chosen from CA (celluloseacetate), CAP (cellulose acetate propionate), CAB (cellulose acetatebutyrate) or CAIB (cellulose acetate isobutyrate), ranging in totaldegree of substitution from 1.0 to 3.0. In one embodiment, the celluloseester is CAP. In embodiments of the invention, the CAP contains 0-5 wt%, 0-2 wt %, 0 to less than 2 wt %, 0-1 wt %, or no added plasticizer.

In embodiments of the invention, the polymer-based resin comprises acellulose ester; and optionally a plasticizer, wherein when theplasticizer is present, the plasticizer is present at less than 20 wt %based on the total weight of the composition, wherein the polymer-basedresin has a heat distortion temperature (“HDT”) that is greater than 90°C., or greater than 95° C., according to ASTM D638 as measured at 1.82MPa using a 1.3 cm×12.7 cm×0.32 cm bar subjected to 50% relativehumidity for 4 hours at 70° C., and wherein when the composition isinjection molded with a barrel temperature of 260° C. with a residencetime of 5 min, the change in the weight average molecular weight(“M_(w)”) is less than 30%.

In certain embodiments, the polymer-based resin comprises a celluloseester and a dispersion of one or more impact modifiers in the celluloseester, in the form of small discrete particles in amounts sufficient toimprove the mechanical and physical properties of the polymer-basedresin, and where the impact modified cellulose ester resin can be meltprocessed.

In one embodiment of the invention, a polymer-based resin is providedcomprising at least one cellulose ester, at least one impact modifier,and optionally, at least one plasticizer. In one embodiment, thecellulose ester is CAP and contains 0-1 wt % plasticizer. In oneembodiment, the cellulose ester is CAP and contains no plasticizer.

In another embodiment of the invention, a cellulose ester composition isprovided comprising at least one cellulose ester, and at least oneimpact modifier and at least one plasticizer. In one embodiment, thecellulose ester is CA and contains 1-15 wt % plasticizer. Inembodiments, the cellulose ester is CA and contains 1-10 wt %, or 1—lessthan 10 wt %, or 1-9 wt % plasticizer.

DETAILED DESCRIPTION

In one aspect of the invention, it is directed to a shaped articlecomprising a polymer-based resin derived from cellulose, wherein thepolymer-based resin has an HDT or at least 90° C., or at least 95° C., abio-derived content of at least 20 wt %, and has at least one of thefollowing properties chosen from: flexural modulus of greater than 1900MPa as measured according to ASTM D790 using a 3.2 mm thick bar hat hasbeen subjected to 50% relative humidity for 48 hours at 23° C.; anotched izod impact strength of greater than 80 J/m as measuredaccording to ASTM D256 using a 3.2 mm thick bar hat has been subjectedto 50% relative humidity for 48 hours at 23° C.; a spiral flow length orat least 3.0 cm, when the polymer-based resin is molded with a spiralflow mold with the conditions of a barrel temperature of 238° C., a melttemperature of 246° C., a molding pressure of 13.8 MPa, a mold thicknessof 0.8 mm, and a mold width of 12.7 mm; a flex creep deflection of lessthan 12 mm, measured using a molded bar having dimensions of 5″ length,0.5″ width, and 0.125″ thickness positioned horizontally on a fixturewith a 4″ span, inside a dry oven for 68 hours at 90° C. with a nominal500 psi stress on the center of the span; a transmission of at least 70measured according to ASTM D1003 using a 3.2 mm plaque after injectionmolding at a barrel set point of 249° C. and a residence time of 5 min;a ΔE value of less than 25, using a 3.2 mm plaque after injectionmolding with a barrel temperature of 249° C. and a residence time of 5min; or an L* color of at least 85, measured according to ASTM E1348using a 3.2 mm plaque after injection molding with a barrel temperatureof 249° C. and a residence time of 5 min. In embodiments, thepolymer-based resin has at least 2, or at least 3 of the listedproperties. In embodiments, the polymer-based resin contains less than 5wt %, or less than 4 wt %, or less than 3 wt %, or less than 2 wt %, orless than 1 wt %, or has no added plasticizer.

In certain embodiments, it is directed to a shaped article comprising apolymer-based resin derived from cellulose, wherein the polymer-basedresin has an HDT or at least 90° C., or at least 95° C., a bio-derivedcontent of at least 20 wt %, a notched Izod impact strength of greaterthan 80 J/m as measured according to ASTM D256 using a 3.2 mm thick barhat has been subjected to 50% relative humidity for 48 hours at 23° C.,and has at least one of the following properties chosen from: flexuralmodulus of greater than 1900 MPa as measured according to ASTM D790using a 3.2 mm thick bar hat has been subjected to 50% relative humidityfor 48 hours at 23° C.; a spiral flow length or at least 3.0 cm, whenthe polymer-based resin is molded with a spiral flow mold with theconditions of a barrel temperature of 238° C., a melt temperature of246° C., a molding pressure of 13.8 MPa, a mold thickness of 0.8 mm, anda mold width of 12.7 mm; a flex creep deflection of less than 12 mm,measured using a molded bar having dimensions of 5″ length, 0.5″ width,and 0.125″ thickness positioned horizontally on a fixture with a 4″span, inside a dry oven for 68 hours at 90° C. with a nominal 500 psistress on the center of the span; a transmission of at least 70 measuredaccording to ASTM D1003 using a 3.2 mm plaque after injection molding ata barrel set point of 249° C. and a residence time of 5 min; a ΔE valueof less than 25, using a 3.2 mm plaque after injection molding with abarrel temperature of 249° C. and a residence time of 5 min; or an L*color of at least 85, measured according to ASTM E1348 using a 3.2 mmplaque after injection molding with a barrel temperature of 249° C. anda residence time of 5 min. In embodiments, the polymer-based resin hasat least 2, or at least 3 of the listed properties. In embodiments, thepolymer-based resin contains less than 5 wt %, or less than 4 wt %, orless than 3 wt %, or less than 2 wt %, or less than 1 wt %, or has noadded plasticizer.

In embodiments of the invention, the polymer-based resin has a heatdistortion temperature (“HDT”) greater than 90° C., or greater than 95°C., according to ASTM D648 as measured at 1.82 MPa using a 3.2 mm thickbar that was subjected to 70° C. for 4 hours. In certain embodiments,the polymer-based resin has a heat distortion temperature (“HDT”) of atleast 95° C., at least 100° C., at least 105° C., or at least 110° C.,or at least 115° C. In certain embodiments, the polymer-based resin hasa heat distortion temperature (“HDT”) in the range from 90° C. to 140°C., 90° C. to 130° C., 90° C. to 120° C., 90° C. to 110° C., 95° C. to140° C., 95° C. to 130° C., 95° C. to 120° C., 95° C. to 110° C., 95° C.to 105° C., 100° C. to 140° C., 100° C. to 130° C., 100° C. to 120° C.,100° C. to 110° C., 105° C. to 140° C., 105° C. to 130° C., 105° C. to120° C., 105° C. to 115° C., 105° C. to 110° C., 110° C. to 140° C.,110° C. to 130° C., 110° C. to 125° C., 110° C. to 120° C., 110° C. to115° C., 115° C. to 140° C., 115° C. to 130° C., 120° C. to 140° C.,120° C. to 130° C., or 120° C. to 125° C.

Bio-sourced products are typically identified through programs such asthe USDA's Bio-Preferred program. These programs use ASTM methodD6866-16 to measure the percentage of “new carbon” in the plasticmaterial to produce the product. “New carbon” is the carbon that comesfrom recently grown plants. That is compared with “old carbon” thatcomes from oil, natural gas or coal. The “new carbon” content in thecellulose based plastics used in the present invention is typically inthe range of 40% to 60%, which reflects the fact that the cellulosebackbone in the cellulosic material comes from trees or cotton.

In embodiments of the invention, the polymer-based resin has abio-derived content of at least 20 wt %, measured according to ASTMmethod D6866-16. In certain embodiments, the polymer-based resin has abio-derived content of at least 25 wt %, or at least 30 wt %, or atleast 35 wt %, or at least 40 wt %, or at least 45 wt %%, measuredaccording to ASTM method D6866-16. In certain embodiments, thepolymer-based resin has a bio-derived content in the range of about 20to about 60 wt %, 20 to 50 wt %, 20 to 45 wt %, 25 to 60 wt %, 25 to 50wt %, 25 to 45 wt %, 30 to 60 wt %, 30 to 50 wt %, 30 to 45 wt %, 35 to60 wt %, 35 to 50 wt %, 35 to 45 wt %, 40 to 60 wt %, 40 to 50 wt %, or40 to 45 wt %%, measured according to ASTM method D6866-16.

In embodiments of the invention, the polymer-based resin has a flexuralmodulus of greater than 1800 MPa as measured according to ASTM D790using a 3.2 mm thick bar hat has been subjected to 50% relative humidityfor 48 hours at 23° C. In certain embodiments, the polymer-based resinhas a flexural modulus of at least 1900 MPa, at least 2000 MPa, at least2100 MPa, at least 2200 MPa, at least 2300 MPa, or at least 2400 MPa, asmeasured according to ASTM D790 using a 3.2 mm thick bar hat has beensubjected to 50% relative humidity for 48 hours at 23° C. In certainembodiments, the polymer-based resin has a flexural modulus is in therange of from about 1800 to about 3500 MPa, from about 1900 to about3500 MPa, from about 2000 to about 3500 MPa, from about 2100 to about3500 MPa, from about 2200 to about 3500 MPa, from about 2300 to about3500 MPa, from about 2400 to about 3500 MPa, or from about 2500 to about3500 MPa, as measured according to ASTM D790 using a 3.2 mm thick barhat has been subjected to 50% relative humidity for 48 hours at 23° C.In certain embodiments, the polymer-based resin has a flexural modulusis in the range of from about 1900 to about 2500 MPa, from about 1900 toabout 2800 MPa, or from about 1900 to about 3000 MPa, as measuredaccording to ASTM D790 using a 3.2 mm thick bar hat has been subjectedto 50% relative humidity for 48 hours at 23° C.

In embodiments of the invention, the polymer-based resin has a notchedizod impact strength of at least 40 J/m, or at least 60 J/m, as measuredaccording to ASTM D256 using a 3.2 mm thick bar hat has been subjectedto 50% relative humidity for 48 hours at 23° C. In certain embodiments,the polymer-based resin has a notched izod impact strength of at least80 J/m, at least 90 J/m, or at least 100 J/m, or at least 110 J/m, or atleast 120 J/m, or at least 130 J/m, or at least 140 J/m, or at least 150J/m, as measured according to ASTM D256 using a 3.2 mm thick bar thathas been subjected to 50% relative humidity for 48 hours at 23° C. Incertain embodiments, the polymer-based resin has a notched izod impactstrength in the range of from about 40 J/m to about 400 J/m, from about40 J/m to about 200 J/m, from about 60 J/m to about 400 J/m, from about60 J/m to about 200 J/m, from about 80 J/m to about 500 J/m, from about80 J/m to about 400 J/m, from about 80 J/m to about 300 J/m, from about80 J/m to about 200 J/m, from 100 J/m to about 500 J/m, from about 100J/m to about 400 J/m, from about 100 J/m to about 300 J/m, or from about100 J/m to about 200 J/m, as measured according to ASTM D256 using a 3.2mm thick bar that has been subjected to 50% relative humidity for 48hours at 23° C.

In embodiments of the invention, the polymer-based resin has a spiralflow length of at least 3.0 cm, when the polymer-based resin is moldedwith a spiral flow mold with the conditions of a barrel temperature of238° C., a melt temperature of 246° C., a molding pressure of 13.8 MPa,a mold thickness of 0.8 mm, and a mold width of 12.7 mm. In certainembodiments, the polymer-based resin has a spiral flow length of atleast 4 cm, or at least 5 cm, when the polymer-based resin is moldedwith a spiral flow mold with the conditions of a barrel temperature of238° C., a melt temperature of 246° C., a molding pressure of 13.8 MPa,a mold thickness of 0.8 mm, and a mold width of 12.7 mm. In certainembodiments, the polymer-based resin has a spiral flow length mold inthe range from about 3.0 cm to about 10.0 cm, from about 4.0 cm to about10.0 cm, from about 5.0 cm to about 10.0 cm, from about 4.0 cm to about9.0 cm, from about 4.0 cm to about 8.0 cm, from about 4.0 cm to about7.0 cm, or from about 5.0 cm to about 7.0 cm, when the polymer-basedresin is molded with a spiral flow mold with the conditions of a barreltemperature of 238° C., a melt temperature of 246° C., a moldingpressure of 13.8 MPa, a mold thickness of 0.8 mm, and a mold width of12.7 mm.

In embodiments of the invention, the polymer-based resin has a flexcreep deflection of less than 12 mm, or less than 11 mm, or less than 10mm, after exposure for 68 hours inside an oven at 90° C. and tested inaccordance with ASTM D2990 using an injection molded bar havingdimensions of 5″ length, 0.5″ width, and 0.125″ thickness positionedhorizontally on a fixture with a 4″ span, with a nominal 500 psi stresson the center of the span. In certain embodiments, the polymer-basedresin has a flex creep deflection in the range from 2 to 12 mm, or 2 to11 mm, or 2 to 10 mm, or 5 to 10 mm, after exposure for 68 hours insidean oven at 90° C. measured using an injection molded bar havingdimensions of 5″ length, 0.5″ width, and 0.125″ thickness positionedhorizontally on a fixture with a 4″ span, with a nominal 500 psi stresson the center of the span.

In embodiments of the invention, the polymer-based resin has atransmission of at least 70, or at least 75, or at least 80, or at least85, or at least 90, measured according to ASTM D1003 using a 3.2 mmplaque after injection molding at a barrel set point of 249° C. and aresidence time of 5 min. In certain embodiments, the polymer-based resinhas transmission in the range from 70 to 95, or 75 to 95, or 80 to 95,or 85 to 95, or 70 to 90, or 75 to 90, or 80 to 90, or 85 to 90,measured according to ASTM D1003 using a 3.2 mm plaque after injectionmolding at a barrel set point of 249° C. and a residence time of 5 min.

In embodiments of the invention, the polymer-based resin has a ΔE valueof less than 25, or less than 20, or less than 15, or less than 14, orless than 13, or less than 12, or less than 11, or less than 10, or lessthan 9, or less than 8, or less than 7, or less than 6, or less than 5,using a 3.2 mm plaque after injection molding with a barrel temperatureof 249° C. and a residence time of 5 min, wherein ΔE is determined bythe following equation: ((L*−100)²+(a*−0)²+(b*−0)²)^(1/2), where the L*,a*, and b* color components were measured according to ASTM E1348. Incertain embodiments, the polymer-based resin has a ΔE value in the rangefrom 2 to 25, or from 2 to 20, or from 2 to 15, or from 2 to 14, or from2 to 13, or from 2 to 12, or from 2 to 11, or from 2 to 10, or from 2 to9, or from 2 to 8, or from 2 to 7, or from 2 to 6, or from 2 to 5, usinga 3.2 mm plaque after injection molding with a barrel temperature of249° C. and a residence time of 5 min, wherein ΔE is determined by thefollowing equation: ((L*−100)²+(a*−0)²+(b*−0)²)^(1/2), where the L*, a*,and b* color components were measured according to ASTM E1348.

In embodiments of the invention, the polymer-based resin has an L* colorof at least 85, or at least 86, or at least 87, or at least 88, or atleast 89, or at least 90, or at least 91, or at least 92, or at least93, or at least 94, or at least 95, measured according to ASTM E1348using a 3.2 mm plaque after injection molding with a barrel temperatureof 249° C. and a residence time of 5 min. In certain embodiments, thepolymer-based resin has an L* color in the range from 85 to 98, or from85 to 97, or from 85 to 96, or from 85 to 95, measured according to ASTME1348 using a 3.2 mm plaque after injection molding with a barreltemperature of 249° C. and a residence time of 5 min.

In embodiments of the invention, the polymer-based resin has a b* valueis less than 15, or less than 12, or less than 10, or less than 9, orless than 8, or less than 7, or less than 6, or less than 5, or lessthan 4, measured according to ASTM E1348 using a 3.2 mm plaque afterinjection molding with a barrel temperature of 249° C. and a residencetime of 5 min. In certain embodiments, the polymer-based resin has a b*color in the range from 0 to 15, or from 0 to 10, or from 0 to 8, orfrom 0 to 5, measured according to ASTM E1348 using a 3.2 mm plaqueafter injection molding with a barrel temperature of 249° C. and aresidence time of 5 min.

In embodiments of the invention, the polymer-based resin has a change inthe absolute weight average molecular weight (“M_(w)”) due to injectionmolding of less than 30%, or less than 25%, or less than 20%, or lessthan 15%, or less than 10%, when the composition is injection moldedwith a barrel temperature of 260° C. with a residence time of 5 min. Incertain embodiments, the polymer-based resin has a change in theabsolute weight average molecular weight (“M_(w)”) due to injectionmolding in the range of 0 to 30%, or 0 to 25%, or 0 to 20%, or 0 to 15%,or 0 to 10%, or 2 to 30%, or 2 to 25%, or 2 to 20%, or 2 to 15%, or 2 to10%, when the composition is injection molded with a barrel temperatureof 260° C. with a residence time of 5 min.

In embodiments of the invention, the polymer-based resin comprises acellulose ester which has an absolute weight average molecular weight inthe range of from about 40,000 Da to about 200,000 Da measured accordingto ASTM D5296 using tetrahydrofuran as a solvent and a flow rate of 1mL/min. In certain embodiments, the cellulose ester has an absoluteweight average molecular weight in the range of from about 50,000 Da toabout 200,000 Da, or 50,000 Da to about 170,000 Da, or 50,000 Da toabout 120,000 Da, or 50,000 Da to about 90,000 Da, or 60,000 Da to about200,000 Da, or 60,000 Da to about 170,000 Da, or 60,000 Da to about120,000 Da, or 60,000 Da to about 90,000 Da, or 90,000 Da to about170,000 Da, or 90,000 Da to about 120,000 Da, or 120,000 Da to about170,000 Da, or 120,000 Da to about 200,000 Da, measured according toASTM D5296 using tetrahydrofuran as a solvent and a flow rate of 1mL/min.

In aspects of this invention, it is directed to shaped articles. Incertain embodiments, the shaped articles are not continuously extrudedfilms that are infinite (or continuous) in one direction and fixed inwidth and thickness in the other two directions, as would be the case ina rolled film. In certain embodiments, a film or sheet can be convertedinto a shaped article, e.g., by thermoforming into a three-dimensionalobject, such as a cup or bowl. In embodiments of the invention, theshaped article is not a film or is not a sheet. In embodiments of theinvention, the shaped articles can be chosen from injection moldedarticles, extrusion molded articles, rotational molded articles,compression molded articles, blow molded articles, injection blow moldedarticles, injection stretch blow molded articles, extrusion blow moldedarticles, sheet or film extrusion articles, profile extrusion articles,gas assist molding articles, structural foam molded articles, orthermoformed articles.

Shaped articles made from polymer-based resins according to the presentinvention can be shaped via molding or extruding for use in thetransportation, appliance, electronics, building and construction,biomedical, packaging, and consumer markets. In embodiments of theinvention, the shaped article is chosen from transparent articles,see-through articles, thin-walled articles, technical articles (e.g.,articles having a complex design), articles having high designspecifications, intricate design articles, articles made from molds thatare difficult to fill under typical molding operations or conditions,wearable articles, body contact articles, containers (includingcontainers for materials intended for body contact), food contactarticles, household articles, general consumer products, packagingarticles, medical articles, or components thereof.

In certain embodiments, the polymer-based resins can be primary moldedinto forms such as pellets, plates, and parisons, or can then also besecondary molded into sheets, thin-wall vessels, or thick-wall vessels.Thin-wall vessels can be processed into trays, blister packs, etc.;thick-wall vessels can be processed into bottles, gardening vessels,etc. Also, the polymer-based resins can be processed into dailynecessaries such as hoses, pipes, etc. as well as industrial materials;cushioning materials, agricultural materials, etc. in the form of foamedbodies; industrial materials such as drainage materials, retainingwalls, frame works, and plant protecting materials as well as vessels(for beverages, foods, mechanical or electrical products, agriculturalproducts, medicines, or seedling pots) as usual moldings; householdgoods such as eating utensils, knives, forks, spoons, trays, wallpapers,facial tissue, wrapping cords, pillows, and expanded beads forcushioning; medical goods; office goods such as cylinder parts of pens,files, tack sheets, and protective films for CDs, electronic devices,and the like; information media materials such as cards; bodies ofoutdoor goods, sporting goods such as golf tees, and leisure goods, etc.

In embodiments, articles can include, for example, enclosures, housings,panels, and parts for outdoor vehicles and devices; enclosures forelectrical and telecommunication devices; outdoor furniture; aircraftcomponents; boats and marine equipment, including trim, enclosures, andhousings; outboard motor housings; depth finder housings; personalwatercraft; jet-skis; pools; spas; hot tubs; steps; step coverings;building and construction applications such as glazing, roofs, windows,floors, decorative window furnishings or treatments; treated glasscovers for pictures, paintings, posters, and like display items; wallpanels, and doors; counter tops; protected graphics; outdoor and indoorsigns; enclosures, housings, panels, and parts for automatic tellermachines (ATM); computer; desk-top computer; portable computer; lap-topcomputer; hand held computer housings; monitor; printer; keyboards; FAXmachine; copier; telephone; phone bezels; mobile phone; radio sender;radio receiver; enclosures, housings, panels, and parts for lawn andgarden tractors, lawn mowers, and tools, including lawn and gardentools; window and door trim; sports equipment and toys; enclosures,housings, panels, and parts for snowmobiles; recreational vehicle panelsand components; playground equipment; shoe laces; articles made fromplastic-wood combinations; golf course markers; utility pit covers;light fixtures; lighting appliances; network interface device housings;transformer housings; air conditioner housings; cladding or seating forpublic transportation; cladding or seating for trains, subways, orbuses; meter housings; antenna housings; cladding for satellite dishes;coated helmets and personal protective equipment; coated synthetic ornatural textiles; coated painted articles; coated dyed articles; coatedfluorescent articles; coated foam articles; and like applications.

In certain embodiments, articles that can be prepared according to theinvention using the polymer-based resins, include, for example,automotive, aircraft, and watercraft exterior and interior components.Articles can include, but are not limited to, instrument panels,overhead consoles, interior trim, center consoles, panels, quarterpanels, rocker panels, trim, fenders, doors, deck lids, trunk lids,hoods, bonnets, roofs, bumpers, fascia, grilles, minor housings, pillarappliqués, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, headlamps, taillamps, tail lamp housings, tail lamp bezels, license plate enclosures,roof racks, circuit breakers, electrical and electronic housings, andrunning boards, automotive bezel, an automobile headlamp lens (e.g., anouter headlamp lens or an inner headlamp lens), or a headlamp assemblycomprising: a headlamp lens; a headlamp reflector; a bezel; and ahousing, or any combination thereof.

In certain embodiments, articles that utilize the polymer-based resinscontaining cellulose esters having higher HDT and improved mechanicalproperties as described herein can include vehicle interior parts (e.g.,door handles, cup holders, dashboards, and glove boxes), appliancecomponents, food and beverage containers, food and beverage containerlids, electrical and electronic device enclosures (e.g., computermonitor enclosures, laptop enclosures, cellular phone enclosures), andthe like, electrical and electronic device enclosures (e.g., computermonitor enclosures, laptop enclosures, cellular phone enclosures), andthe like.

Additional examples of articles include disposable knives, forks,spoons, plates, cups, straws as well as eyeglass frames, toothbrushhandles, toys, automotive trim, tool handles, camera parts, parts ofelectronic devices, razor parts, ink pen barrels, disposable syringes,bottles, and the like. In one embodiment, the compositions of thepresent invention are useful as plastics, films, and sheets. Inembodiments, the compositions described herein are useful as plastics tomake bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery,cutlery handles, shelving, shelving dividers, electronics housing,electronic equipment cases, computer monitors, printers, keyboards,pipes, automotive parts, automotive interior parts, automotive trim,signs, thermoformed letters, siding, toys, thermally conductiveplastics, ophthalmic lenses, tools, tool handles, utensils. In anotherembodiment, the compositions of the present invention described hereinare suitable for use as films, sheeting, molded articles, medicaldevices, packaging, bottles, bottle caps, eyeglass frames, cutlery,disposable cutlery, cutlery handles, shelving, shelving dividers,furniture components, electronics housing, electronic equipment cases,computer monitors, printers, keyboards, pipes, toothbrush handles,automotive parts, automotive interior parts, automotive trim, signs,outdoor signs, skylights, multiwall film, thermoformed letters, siding,toys, toy parts, thermally conductive plastics, ophthalmic lenses andframes, tools, tool handles, and utensils, healthcare supplies,commercial foodservice products, boxes, film for graphic artsapplications, and plastic film for plastic glass laminates.

The cellulose ester compositions described herein are useful in formingfilms, molded articles, and sheeting. The methods of forming thecellulose ester compositions into films, molded articles, and sheetingcan be according to methods known in the art. Examples of potentialmolded articles include without limitation: medical devices, medicalpackaging, healthcare supplies, commercial foodservice products such asfood pans, tumblers and storage boxes, bottles, food processors, blenderand mixer bowls, utensils, water bottles, crisper trays, washing machinefronts, vacuum cleaner parts and toys. Other potential molded articlescould include ophthalmic lenses and frames.

The invention further relates to articles of manufacture comprising thefilm(s) and/or sheet(s) containing cellulose ester compositionsdescribed herein. In embodiments, the films and/or sheets of the presentinvention can be of any thickness which would be apparent to one ofordinary skill in the art.

The invention further relates to the film(s) and/or sheet(s) describedherein. The methods of forming the cellulose ester compositions intofilm(s) and/or sheet(s) can include known methods in the art. Examplesof film(s) and/or sheet(s) of the invention including but not limited toextruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s),compression molded film(s) and/or sheet(s). Methods of making filmand/or sheet include but are not limited to extrusion, compressionmolding, wet block processing, and dry block processing.

As discussed herein, in certain embodiments of the invention, thepolymer-based resins comprise at least one cellulose ester.

In embodiments, the cellulose ester utilized in this invention can beany that is known in the art. Cellulose esters that can be used for thepresent invention generally comprise repeating units of the structure:

wherein R¹, R², and R³ are selected independently from the groupconsisting of hydrogen or straight chain alkanoyl having from 2 to 10carbon atoms. For cellulose esters, the substitution level is usuallyexpressed in terms of degree of substitution (DS), which is the averagenumber of non-OH substitutents per anhydroglucose unit (AGU). Generally,conventional cellulose contains three hydroxyl groups in each AGU unitthat can be substituted; therefore, DS can have a value between zero andthree. However, low molecular weight cellulose mixed esters can have atotal degree of substitution slightly above 3, due to end groupcontributions. Native cellulose is a large polysaccharide with a degreeof polymerization from 250-5,000 even after pulping and purification,and thus the assumption that the maximum DS is 3.0 is approximatelycorrect. However, as the degree of polymerization is lowered, as in lowmolecular weight cellulose mixed esters, the end groups of thepolysaccharide backbone become relatively more significant, therebyresulting in a DS that can range in excess of 3.0. Low molecular weightcellulose mixed esters are discussed in more detail subsequently in thisdisclosure. Because DS is a statistical mean value, a value of 1 doesnot assure that every AGU has a single substitutent. In some cases,there can be unsubstituted anhydroglucose units, some with two and somewith three substitutents, and typically the value will be a non-integer.Total DS is defined as the average number of all of substituents peranhydroglucose unit. The degree of substitution per AGU can also referto a particular substitutent, such as, for example, hydroxyl, acetyl,butyryl, or propionyl.

In embodiments, the cellulose ester utilized can be a cellulose triesteror a secondary cellulose ester. Examples of cellulose triesters include,but are not limited to, cellulose triacetate, cellulose tripropionate,or cellulose tributyrate. Examples of secondary cellulose esters includecellulose acetate, cellulose acetate propionate, and cellulose acetatebutyrate.

In one embodiment of the invention, the cellulose ester can be chosenfrom cellulose acetate (CA), cellulose propionate (CP), cellulosebutyrate (CB), cellulose acetate propionate (CAP), cellulose acetatebutyrate (CAB), cellulose propionate butyrate (CPB), and the like, orcombinations thereof. Examples of such cellulose esters are described inU.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147,2,129,052; and 3,617,201, incorporated herein by reference in theirentirety to the extent that they do not contradict the statementsherein.

In embodiments of the invention, the cellulose esters have at least 2anhydroglucose rings and can have between at least 50 and up to 5,000anhydroglucose rings. The number of anhydroglucose units per molecule isdefined as the degree of polymerization (DP) of the cellulose ester. Inembodiments, cellulose esters can have an inherent viscosity (IV) ofabout 0.2 to about 3.0 deciliters/gram, or about 0.5 to about 1.8, orabout 1 to about 1.5, as measured at a temperature of 25° C. for a 0.25gram sample in 100 ml of a 60/40 by weight solution ofphenol/tetrachloroethane. Examples of cellulose esters include, but arenot limited to, cellulose acetate, cellulose propionate, cellulosebutyrate, cellulose acetate propionate (CAP), cellulose acetate butyrate(CAB), cellulose propionate butyrate, and the like. In embodiments,cellulose esters useful herein can have a DS/AGU of about 2 to about2.99, and the substituting ester can comprise either acetyl, propionyland butyryl, or any combinations of these. In another embodiment of theinvention, the total DS/AGU ranges from about 2 to about 2.99 and theDS/AGU of acetyl ranges from about 0 to 2.2, with the remainder of theester groups comprising propionyl, butyryl or combinations thereof.

Cellulose esters can be produced by any method known in the art.Examples of processes for producing cellulose esters are taught inKirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5,Wiley-Interscience, New York (2004), pp. 394-444. Cellulose, thestarting material for producing cellulose esters, can be obtained indifferent grades and sources such as from cotton linters, softwood pulp,hardwood pulp, corn fiber and other agricultural sources, and bacterialcellulose, among others.

One method of producing cellulose esters is esterification of thecellulose by mixing cellulose with the appropriate organic acids, acidanhydrides, and catalysts. Cellulose is then converted to a cellulosetriester. Ester hydrolysis is then performed by adding a water-acidmixture to the cellulose triester, which can then be filtered to removeany gel particles or fibers. Water is then added to the mixture toprecipitate the cellulose ester. The cellulose ester can then be washedwith water to remove reaction by-products followed by dewatering anddrying.

The cellulose triesters to be hydrolyzed can have three substitutentsselected independently from alkanoyls having from 2 to 10 carbon atoms.Examples of cellulose triesters include cellulose triacetate, cellulosetripropionate, and cellulose tributyrate or mixed triesters of cellulosesuch as cellulose acetate propionate, and cellulose acetate butyrate.These cellulose esters can be prepared by a number of methods known tothose skilled in the art. For example, cellulose esters can be preparedby heterogeneous acylation of cellulose in a mixture of carboxylic acidand anhydride in the presence of a catalyst such as H₂SO₄. Cellulosetriesters can also be prepared by the homogeneous acylation of cellulosedissolved in an appropriate solvent such as LiCl/DMAc or LiCl/NMP.

Those skilled in the art will understand that the commercial term ofcellulose triesters also encompasses cellulose esters that are notcompletely substituted with acyl groups. For example, cellulosetriacetate commercially available from Eastman Chemical Company,Kingsport, Tenn., U.S.A., typically has a DS from about 2.85 to about2.99.

After esterification of the cellulose to the triester, part of the acylsubstitutents can be removed by hydrolysis or by alcoholysis to give asecondary cellulose ester. As noted previously, depending on theparticular method employed, the distribution of the acyl substituentscan be random or non-random. Secondary cellulose esters can also beprepared directly with no hydrolysis by using a limiting amount ofacylating reagent. This process is particularly useful when the reactionis conducted in a solvent that will dissolve cellulose. All of thesemethods yield cellulose esters that are useful in this invention.

In one embodiment, the secondary cellulose esters useful in the presentinvention have an absolute weight average molecular weight (Mw) fromabout 5,000 to about 400,000 as measured by gel permeationchromatography (GPC) according to ASTM D6474. The following method isused to calculate the absolute weight average molecular weight values(Mw) for CE. The solvent is THF stabilized with BHT Preservative. Theinstrumentation for the THF/cellulose ester procedure consists of thefollowing Agilent 1200 series components: degasser, isocratic pump,auto-sampler, column oven, UV/Vis detector and a refractive indexdetector. The test temperature is 30° C. and flow rate is 1.0 ml/min. Asample solution of 25 mg cellulose ester in 10 ml THF with BHTpreservative and 10 μl toluene flow rate marker is made. The injectionvolume is 50 μl. The column set is Polymer Laboratories 5 μm PLgel,Guard+Mixed C+Oligopore. The detection is by refractive index. Thecalibrants are monodisperse polystyrene standards, Mw=580 to 3,220,000from Polymer Laboratories. The universal calibration parameters are asfollows: PS (K=0.0001280 and a=0.7120) and CE (K=0.00007572 anda=0.8424). The universal calibration parameters above were determined bylight scattering and viscometery to yield the correct weight averagemolecular weights. In a further embodiment, the Mw is from about 15,000to about 300,000. In yet further embodiments, the Mw ranges from about10,000 to about 250,000; from about 15000 to 200000; from about 20,000to about 150,000; from about 50,000 to about 150,000, or from about70,000 to about 120,000.

The most common commercial secondary cellulose esters are prepared byinitial acid catalyzed heterogeneous acylation of cellulose to form thecellulose triester. After a homogeneous solution in the correspondingcarboxylic acid of the cellulose triester is obtained, the cellulosetriester is then subjected to hydrolysis until the desired degree ofsubstitution is obtained. After isolation, a random secondary celluloseester is obtained. That is, the relative degree of substitution (RDS) ateach hydroxyl is roughly equal.

Some examples of cellulose esters that can be useful in the presentinvention can be prepared using techniques known in the art and can beobtained from Eastman Chemical Company, Kingsport, Tenn., U.S.A., e.g.,Eastman™ Cellulose Acetate Propionate CAP 482-20, Eastman™ CelluloseAcetate Propionate CAP 141-20, Eastman™ Cellulose Acetate Butyrate CAB381-20, Cellulose Acetate Butyrate CAB 171-15 and Eastman™ CelluloseAcetate CA 398-30.

In embodiments, the cellulose esters utilized in this invention can alsocontain chemical functionality and are described herein as eitherderivatized, modified, or functionalized cellulose esters.Functionalized cellulose esters can be produced by reacting the freehydroxyl groups of cellulose esters with a bifunctional reactant thathas one linking group for grafting to the cellulose ester and onefunctional group to provide a new chemical group to the cellulose ester.Examples of such bifunctional reactants include succinic anhydride whichlinks through an ester bond and provides acid functionality;mercaptosilanes which links through alkoxysilane bonds and providesmercapto functionality; and isocyanotoethyl methacrylate which linksthrough a urethane bond and gives methacrylate functionality.

In one embodiment of the invention, functionalized cellulose esters areproduced by reacting the free hydroxyl groups of the cellulose esterswith a bifunctional reactant producing a cellulose ester with at leastone functional group selected from the group consisting of unsaturation(double bonds), carboxylic acids, acetoacetate, acetoacetate imide,mercapto, melamine, and long alkyl chains.

In one embodiment of the invention, the cellulose ester can be chosenfrom cellulose propionate (CP), cellulose butyrate (CB), celluloseacetate propionate (CAP), cellulose acetate butyrate (CAB), cellulosepropionate butyrate (CPB), cellulose tripropionate (CTP), or cellulosetributyrate (CTB), but not from cellulose acetate (CA).

In embodiments, the polymer-based resin in accordance with the inventioncomprises a cellulose ester; and optionally a plasticizer, wherein whenthe plasticizer is present, the plasticizer is present at less than 20wt % based on the total weight of the resin, wherein the resin has aheat distortion temperature that is in the range of from about 90° C. toabout 140° C. according to ASTM D648 as measured at 1.82 MPa using a 3.2mm thick bar subjected to 70° C. for 4 hours, and wherein the change inthe weight average molecular weight (“M_(w)”) due to injection moldingis less than 30%, when the resin is injection molded with a barreltemperature of 260° C. with a residence time of 5 min.

In certain embodiments, where the polymer-based resin is a celluloseester composition, the change in the weight average molecular weight(“M_(w)”) due to injection molding is less than 25%, or less than 20%,or less than 15%, or less than 10%, when the resin is injection moldedwith a barrel temperature of 260° C. with a residence time of 5 min. Incertain embodiments, the change in the weight average molecular weight(“M_(w)”) due to injection molding is in the range from 0 to 25%, orfrom 0 to 20%, or from 0 to 15%, or from 0 to 10%, when the resin isinjection molded with a barrel temperature of 260° C. with a residencetime of 5 min.

In embodiments, where the polymer-based resin comprises a celluloseester composition, the shaped article has low birefringence resulting inthe substantial elimination of an unwelcomed rainbow effect that someplastics (e.g., engineered plastics) experience with polarized light.This low birefringence can improve the user experience with electronicdevice screens and retail displays. In embodiments, the shaped articlesin accordance with the invention have a birefringence very close toarticles molded with PMMA (e.g., articles molded with Evonik CYROAcrylite H12) and significantly lower than articles molded withpolyesters (e.g., Eastman Tritan TX1501HF) or polycarbonates (e.g.,Covestro Makrolon 2458).

In embodiments, a salt stabilizer can be incorporated into the celluloseester composition to stabilize the cellulose ester composition duringprocessing. The cation component of the salt stabilizer is chosen fromaluminum, calcium, magnesium, copper, cobalt, manganese, barium,strontium, zinc, tin, cadmium, chromium and iron cations; and the anioncomponent of the salt stabilizer is an (C₆₋₂₀)alicyclic carboxylic acid,a (C₆₋₂₀)alkyl carboxylic acid, or a (C₆₋₂₀)alkenyl carboxylic acid.Examples of the (C₆₋₂₀)alicyclic carboxylic acid, the (C₆₋₂₀)alkylcarboxylic acid, or the (C₆₋₂₀)alkenyl carboxylic acid includenaphthenic acid, abietic acid, cyclohexane carboxylic acid, cyclohexanepropionic acid, 3-methyl-cyclopentyl acetic acid, 4-methylcyclohexanecarboxylic acid, 2,2,6-trimethylcyclohexane carboxylic acid,2,3-dimethylcyclopentyl acetic acid, 2-methylcyclopentyl propionic acid,palmitic acid, stearic acid, oleic acid, lauric acid, and the like.Examples of the salt stabilizers include strontium naphthenate, coppernaphthenate, magnesium naphthenate, copper abietate, magnesium abietate,and the like.

In one embodiment, the cellulose ester composition further comprises asalt stabilizer in the range of from about 0.01 wt % to about 0.5 wt %based on the total weight of the composition. In one embodiment, thecellulose ester composition further comprises a salt stabilizer in therange of from about 0.01 wt % to about 0.4 wt % based on the totalweight of the composition. In one embodiment, the cellulose estercomposition further comprises a salt stabilizer in the range of fromabout 0.01 wt % to about 0.3 wt % based on the total weight of thecomposition. In one embodiment, the cellulose ester composition furthercomprises a salt stabilizer in the range of from about 0.01 wt % toabout 0.2 wt % based on the total weight of the composition. In oneembodiment, the cellulose ester composition further comprises a saltstabilizer in the range of from about 0.1 wt % to about 0.3 wt % basedon the total weight of the composition. In one embodiment, the celluloseester composition further comprises a salt stabilizer in the range offrom about 0.01 wt % to about 0.1 wt % based on the total weight of thecomposition.

In embodiments of the invention, the polymer-based resin, e.g., wherethe polymer-based resin is a cellulose ester composition, can compriseantioxidants and acid stabilizers. Antioxidants are chemicals used tointerrupt degradation processes during the processing of materials.Antioxidants are classified into several classes, including primaryantioxidant, and secondary antioxidant.

“Primary antioxidants” are antioxidants that act by reacting withperoxide radicals via a hydrogen transfer to quench the radicals.Primary antioxidants generally contain reactive hydroxy or amino groupssuch as in hindered phenols and secondary aromatic amines. Examples ofprimary antioxidants include Irganox™ 1010, 1076, 1726, 245, 1098, 259,and 1425; Ethanox™ 310, 376, 314, and 330; Evernox™ 10, 76, 1335, 1330,3114, MD 1024, 1098, 1726, 120, 2246, and 565; Anox™ 20, 29, 330, 70,IC-14, and 1315; Lowinox™ 520, 1790, 22IB46, 22M46, 44625, AH25, GP45,CA22, CPL, HD98, TBM-6, and WSP; Naugard™ 431, PS48, SP, and 445;Songnox™ 1010, 1024, 1035, 1076 CP, 1135 LQ, 1290 PW, 1330FF, 1330PW,2590 PW, and 3114 FF; and ADK Stab AO-20, AO-30, AO-40, AO-50, AO-60,AO-80, and AO-330.

In one embodiment, the composition further comprises a primaryantioxidant in the range of from 0 to about 1.0 wt % based on the totalweight of the composition. In certain embodiments, the compositionfurther comprises a primary antioxidant in the range of from about 0.1to about 1.0 wt %, or from about 0.2 to about 1.0 wt %, or from about0.3 to about 1.0 wt %, or about 0.4 to about 1.0 wt %, or from about 0.5to about 1.0 wt %, or from about 0.6 to about 1.0 wt %, or from about0.7 to about 1.0 wt %, or from about 0.8 to about 1.0 wt %, based on thetotal weight of the composition. In certain embodiments, the compositionfurther comprises a primary antioxidant in the range of from about 0.1to about 0.8 wt %, or from about 0.1 to about 0.6 wt %, or from about0.1 to about 0.4 wt %, based on the total weight of the composition.

“Secondary antioxidants” are often called hydroperoxide decomposers.They act by reacting with hydroperoxides to decompose them intononreactive and thermally stable products that are not radicals. Theyare often used in conjunction with primary antioxidants. Examples ofsecondary antioxidants include the organophosphorous (e.g., phosphites,phosphonites) and organosulfur classes of compounds. The phosphorous andsulfur atoms of these compounds react with peroxides to convert theperoxides into alcohols. Examples of secondary antioxidants includeUltranox 626, Ethanox™ 368, 326, and 327; Doverphos™ LPG11, LPG12, DPS-680, 4, 10, S480, and S-9228; Evernox™ 168 and 626; Irgafos™ 126 and168; Weston™ DPDP, DPP, EHDP, PDDP, TDP, TLP, and TPP; Mark™ CH 302, CH55, TNPP, CH66, CH 300, CH 301, CH 302, CH 304, and CH 305; ADK Stab2112, HP-10, PEP-8, PEP-36, 1178, 135A, 1500, 3010, C, and TPP; Weston439, DHOP, DPDP, DPP, DPTDP, EHDP, PDDP, PNPG, PTP, PTP, TDP, TLP, TPP,398, 399, 430, 705, 705T, TLTTP, and TNPP; Alkanox 240, 626, 626A,627AV, 618F, and 619F; and Songnox™ 1680 FF, 1680 PW, and 6280 FF.

In embodiments, the composition further comprises a secondaryantioxidant in the range of from about 0.1 to about 0.8 wt %, or fromabout 0.2 to about 0.8 wt %, or from about 0.3 to about 0.8 wt %, orfrom about 0.4 to about 0.8 wt %, or from about 0.5 to about 0.8 wt %,or from about 0.6 to about 0.8 wt %, based on the total weight of thecomposition. In certain embodiments, the composition further comprises asecondary antioxidant in the range of from about 0.1 to about 0.7 wt %,or from about 0.1 to about 0.6 wt %, or from about 0.1 to about 0.5 wt%, or from about 0.1 to about 0.4 wt %, or from about 0.1 to about 0.3wt %, based on the total weight of the composition. In certainembodiment, the composition further comprises a secondary antioxidant inthe range of from about 0.3 to about 0.7 wt %, or from about 0.3 toabout 0.6 wt %, based on the total weight of the composition.

“Acid scavengers” are additives that neutralize acids formed during theprocessing of polymers. Examples of acid scavengers include Hycite 713;Kisuma DHT-4A, DHT-4V, DHT-4A-2, DHT-4C, ZHT-4V, and KW2200; BrueggemannChemical Zinc Carbonate RAC; Sipax™ AC-207; calcium stearate; BaerlocherGL 34, RSN, GP, and LA Veg; Licomont CAV 102; FACI Calcium Stearate DW,PLC, SP, and WLC; Hangzhou Hitech Fine Chemical: CAST, and ZnST;Songstab™ SC-110, SC-120, SC-130, SM-310, and SZ-210; Sun Ace SAK-CS,SAK-DSC, SAK-DMS, SAK-DZS, and SAK-KS; US Zinc Zinc Oxide 201, 205 HAS,205H, 210, and 210E; Drapex™ 4.4, 6.8, 39, 391, 392, and 392S; Vikoflex™4050, 5075, 7170, 7190, 7040, 9010, 9040, and 9080; Joncryl™ ADR 4468,and ADR 4400; Adeka CIZER D-32; Epon™ 1001F, 1002F, and 1007F;Aralidite™ ECN 1299, 1273, 1280, 1299, and 9511; Dynamar RC 5251Q; andNexamite PBO.

In embodiments, the composition further comprises an acid scavenger inthe range of from about 0.2 to about 2.0 wt %, or from about 0.4 toabout 2.0 wt %, or from about 0.6 to about 2.0 wt %, or from about 0.8to about 2.0 wt %, or from about 1.0 to about 2.0 wt %, or from about1.2 to about 2.0 wt %, or from about 1.4 to about 2.0 wt %, or fromabout 1.6 to about 2.0 wt %, or from about 1.8 to about 2.0 wt %, basedon the total weight of the composition. In certain embodiments, thecomposition further comprises an acid scavenger in the range of fromabout 0.2 to about 1.8 wt %, or from about 0.2 to about 1.6 wt %, orfrom about 0.2 to about 1.4 wt %, or from about 0.2 to about 1.2 wt %,or from about 0.2 to about 1.0 wt %, or from about 0.2 to about 0.8 wt%, or from about 0.2 to about 0.6 wt %, or from about 0.2 to about 0.4wt %, based on the total weight of the composition. In certainembodiments, the composition further comprises an acid scavenger in therange of from about 0.4 to about 1.8 wt %, or from about 0.6 to about1.6 wt %, or from about 0.8 to about 1.4 wt %, or from about 0.8 toabout 1.2 wt %, based on the total weight of the composition.

In one embodiment, the composition further comprises a secondaryantioxidant in the range of from about 0.1 to about 0.8 wt % based onthe total weight of the composition; and an acid scavenger in the rangeof from about 0.2 to about 2.0 wt % based on the total weight of thecomposition.

In one embodiment, the composition further comprises a primaryantioxidant in the range of from about 0 to about 1.0 wt % based on thetotal weight of the composition; a secondary antioxidant in the range offrom about 0.1 to about 0.8 wt % based on the total weight of thecomposition; and an acid scavenger in the range of from about 0.2 toabout 2.0 wt % based on the total weight of the composition.

In one embodiment, the composition further comprises a secondaryantioxidant in the range of from about 0.1 to about 0.8 wt % based onthe total weight of the composition; an acid scavenger in the range offrom about 0.2 to about 2.0 wt % based on the total weight of thecomposition; and an impact modifier in the range of from 0 to about 15wt % based on the total weight of the composition.

In one embodiment, the composition further comprises a primaryantioxidant in the range of from about 0 to about 1.0 wt % based on thetotal weight of the composition; a secondary antioxidant in the range offrom about 0.1 to about 0.8 wt % based on the total weight of thecomposition; an acid scavenger in the range of from about 0.2 to about2.0 wt % based on the total weight of the composition; and an impactmodifier in the range of from 0 to about 15 wt % based on the totalweight of the composition.

In embodiments of the invention, the impact modifier can be any materialfound to increase the impact strength of cellulose ester compositions.For purposes of this invention, an impact modifier is defined as anymaterial in which at least one portion of its composition is anelastomer with a glass transition temperature (Tg) below roomtemperature. Tg can be measured for example according to ASTM D3418using a TA 2100 Thermal Analyst Instrument using a scan rate of 20°C./min. Several classes of impact modifier fit this description. In oneembodiment, the composition further comprises an impact modifier in therange of from 0 to about 15 wt % based on the total weight of thecomposition.

In one embodiment, the impact modifier can be selected from the class ofmaterials known as modified polyolefins. In this class, the olefin iscopolymerized with additional monomers that limit the crystallization ofthe polymer and increase the amount of the chain with Tg below roomtemperature and reduce the modulus below 500 MPa. Examples of modifiedolefins include EMA (examples include Elvaloy 4051, Lotader 3410 andLotader 8900), EBA, EVA (examples include Levamelt 500, Levamelt 600,Levamelt 700, Levamelt 800, Elvax 40W, Evatane 28-40, Evatane 40-55,Evatane 18-150, Bynel E418 and Bynel 3101), EEA, EPDM (examples includeRoyaltuf 498), EPR, etc.

In one class of the embodiment, the impact modifier is a block copolymerin which at least one segment of the chain has a Tg below roomtemperature, referred to as the soft segment, and at least one segmentof the chain has a Tg or Tm above room temperature, referred to as thehard segment. These block copolymers are also commonly referred to asthermoplastic elastomers (TPEs). Examples of block compolymers of thisclass include styrenic materials such as SBS, SEBS, and SIS (examplesinclude Kraton G1657MS, Kraton FG1901 G and Kraton FG1924 G);thermoplastic urethanes (TPU) (examples include Elastolan 1170Z, Estane2355, Estane ALR CL87A and Estane ALR 72A); polyester-ether copolymers(examples include Ecdel 9966 and Hytrel 3078) or polyamide-ethercopolymers (examples include Pebax 5533).

In one embodiment, the impact modifier can be selected from the class ofemulsion-prepared materials known as core-shell impact modifiers. In oneembodiment, the impact modifier is a MBS core-shell impact modifier suchas a methacrylate-butadiene-styrene that has a core made out ofbutadiene-styrene copolymers and shell made out of methylmethacrylate-styrene copolymer. In another embodiment, the impactmodifier is an acrylic core-shell impact modifier that has a core madeout of an acrylic polymer and shell from made frompolymethylmethacrylate, such as methyl methacrylate-butyl acrylate.

In one embodiment of the invention, the core shell impact modifier is anMBS impact modifier that can comprise:

(A) from about 70 to about 85 parts of a core comprising from about 15to about 35 percent by weight of units derived from at least one vinylaromatic monomer, and from about 65 to about 85 percent by weight ofunits derived from at least one diolefin monomer;(B) from about 8 to about 14 parts of an inner graft stage comprising atleast one vinyl aromatic monomer or at least one C1-C4 alkylmethacrylate monomer;(C) from about 0.1 to about 5 parts of an intermediate sealer stagecomprising at least one monomer selected from a C1-C8 alkyl acrylate ora polyunsaturated crosslinker; and(D) from about 10 to about 16 parts of an outer shell comprising atleast one C1-C4 alkyl (meth)acrylate monomers or at least one vinylaromatic monomer.

In embodiments, the MBS impact modifier can comprise graft polymercompositions comprising 10 to 70 percent by weight of a polymer or acopolymer of butadiene and grafts of firstly methyl(meth)acrylate andcrosslinker, and secondly of styrene, and thirdly ofmethyl(meth)acrylate with an optional cross-linker.

Monomers suitable for polymerization with the conjugated diolefin andpreferably with butadiene, can include alkenyl aromatic compounds andpreferably vinyl aromatic compounds such as styrene, divinylbenzene,alpha-methyl styrene, vinyl toluene, hydrogenated styrene; lower (CZ-Cu)alkyl acrylates such as ethyl acrylate, n-propylacrylate, n-butylacrylate, Z-methylbutylacrylate, 3-methylbutyl acrylate, amylacrylate,n-hexylacrylate, Z-ethylhexyl acrylate; lower (C2-C12)alkyl(meth)acrylates; acrylonitriles; olefins; and the like; or acombination of any of the foregoing.

Suitable cross-linking agents include divinylbenzene; di(meth)acrylates;diacrylates such as the diacrylate of mono-, di- or polyethylene glycol;their (meth)acrylates; divinyl sulfide; divinyl ether; vinyl acrylate;vinyl(meth)acrylate; trivinylbenzene; trimethylolpropane;tri(meth)acrylate; triallyl cyanurate and triallyl isocyanurate.

In one embodiment, the MBS core-shell impact modifier can comprise acopolymer of butadiene and styrene or a terpolymer of butadiene,styrene, and divinylbenzene. Although the relative amounts of themonomers which comprise the copolymeric substrate may vary, thebutadiene component will typically comprise from about 30 to 100 partsby weight, the styrene component can comprise from 0 to about 70 partsby weight, and the divinylbenzene component can comprise from 0 to about5 parts by weight based upon 100 parts by weight of butadiene, styrene,and divinylbenzene combined. In an embodiment, the copolymer substratecan comprise from about 50 to about 90 parts by weight of butadiene,from about 10 to about 50 parts by weight of styrene, and from 0 toabout 5 parts by weight of divinylbenzene on the same basis, or fromabout 65 to about 85 parts by weight of butadiene, from about 15 toabout 35 parts by weight of styrene, and from about 0.5 to about 2.0parts by weight of divinylbenzene on the same basis.

Examples of methacrylate-butadiene-styrene core shell polymers are thosedescribed in, but not limited to, patents U.S. Pat. Nos. 4,446,585,5,534,594, and 6,331,580. MBS core-shell impact modifiers can beobtained as Kane Ace B564 from Kaneka, Clearstrength from Arkema,Paraloid from Dow, and Visiomer from Evonik.

In one class of this embodiment, the impact modifier is an ABScore-shell impact modifier. Examples of ABS core-shell impact modifiersinclude an acrylonitrile-butadiene-styrene ABS core-shell impactmodifier that has a core made out of butadiene-styrene copolymers andshell made out of acrylonitrile-styrene copolymer.

In one embodiment of the present invention, the core shell impactmodifier is an acrylic impact modifier comprising about 25 to 95 weightpercent of a first elastomeric phase polymerized from a monomer systemcomprising about 75 to 99.8 percent by weight of a (C₁ to C₆) alkylacrylate, 0.1 to 5 percent by weight cross-linking monomer, and 0.1 to 5percent by weight graft linking monomer, and about 75 to 5 weightpercent of a final, rigid thermoplastic phase free of epoxy groupspolymerized in the presence of said elastomeric phase.

Examples of useful acrylates are methyl acrylate, ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate and the like. In some embodiments, theacrylates are n-butyl acrylate and ethyl acrylate.

Examples of acrylic core shell polymers are those described in, but notlimited to, patents U.S. Pat. Nos. 3,448,173, 3,655,825, and 3,853,968.Examples of suitable acrylic impact modifiers are Kane Ace EC0100 fromKaneka, Durastrength from Arkema, Elvaloy and Elvaloy HP from DuPont,and Paraloid from Dow.

In one embodiment, the impact modifier has a relatively neutral pH(e.g., pH between 6 and 8, preferably between 6.5 and 7.5). It isbelieved that this will help prevent the cellulose esters from degradingduring the melt processing of the compositions.

In another embodiment, the refractive index (RI) of the impact modifiersis sufficiently close to that of the cellulose esters to provide acomposition with high transmission and low haze. In one embodiment, theacrylic impact modifiers have a RI that close to the RI of the celluloseester of about 1.46-1.50 to provide clear compositions. In embodiments,the impact modifier and cellulose ester components have a difference inrefractive index, RI(second component)-RI(first component) (e.g., RI ofCE-RI of impact modifier), of about 0.006 to about −0.0006, and theimmiscible blend has a percent transmittance of at least 75%, and a hazeof 10% or less more preferably 5% or less.

In embodiments, the composition further comprising the impact modifierhas a percent transmittance of at least 75%, or at least 80%, or atleast 85%, or at least 90%, or at least 95%. In one class of thisembodiment, the composition further comprising the impact modifier has apercent haze of less than 10%. In embodiments, the composition furthercomprising the impact modifier has a percent haze of less than 8%, orless than 6%, or less than 5%.

In one embodiment, the impact modifier can be either a non-reactiveimpact modifier or a reactive impact modifier, or combination of both.It is believed that certain impact modifiers can also improve mechanicaland physical properties of the cellulose ester compositions.

In one embodiment, where non-reactive impact modifiers are utilized, theimpact modifier contains a first polymeric chain segment that is morechemically or physically compatible with the cellulose ester thananother polymeric chain segment. In an embodiment, the first segmentcontains polar functional groups, which provide compatibility with thecellulose ester, including, but not limited to, such polar functionalgroups as ethers, esters, amides, alcohols, amines, ketones and acetals.Compatibility is defined by the preferential interaction of the firstpolymer chain segment with the cellulose ester polymer relative to thesecond segment and can mean molecular scale or microscale interactions.In one embodiment, the first segment is polyethylenevinyl acetate;polyoxyethylene or polyvinyl alcohol.

In embodiments, the second segment can be either saturated orunsaturated hydrocarbon groups or contain both saturated and unsaturatedhydrocarbon groups. The second segment can be an oligomer or a polymer.In one embodiment of the invention, the second segment of thenon-reactive impact modifier is selected from the group consisting ofpolyolefins, polydienes, polyaromatics, and copolymers. An example of apolyaromatic second segment is polystyrene. An example of a copolymersecond segment is styrene/butadiene copolymer.

Examples of non-reactive impact modifiers include, but are not limitedto, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fattyacids, polyethylenevinyl acetate, block polymers of propylene oxide andethylene oxide, ethylene/propylene terpolymers, functionalizedpolyolephins, polyglycerol esters, polysaccharide esters, and sorbitanesters. Examples of ethoxylated alcohols are C₁₁-C₁₅ secondary alcoholethoxylates, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,and C₁₂-C₁₄ natural liner alcohol ethoxylated with ethylene oxide.C₁₁-C₁₅ secondary ethyoxylates can be obtained as Dow Tergitol® 15S fromthe Dow Chemical Company. Polyoxyethlene cetyl ether and polyoxyethylenestearyl ether can be obtained from ICI Surfactants under the Brij®series of products. C₁₂-C₁₄ natural linear alcohol ethoxylated withethylene oxide can be obtained from Hoechst Celanese under the Genapol®series of products. Examples of ethoxylated alkylphenols includeoctylphenoxy poly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxy poly(ethyleneoxy)ethanol can beobtained as Igepal® CA series of products from Rhodia, and nonylphenoxypoly(ethyleneoxy)ethanol can be obtained as Igepal CO series of productsfrom Rhodia or as Tergitol® NP from Dow Chemical Company. Ethyoxylatedfatty acids can include polyethyleneglycol monostearate or monolaruatewhich can be obtained from Henkel under the Nopalcol® series ofproducts. Block polymers of propylene oxide and ethylene oxide can beobtained under the Pluronic® series of products from BASF. Polyglycerolesters can be obtained from Stepan under the Drewpol® series ofproducts. Polysaccharide esters can be obtained from Henkel under theGlucopon® series of products, which are alkyl polyglucosides. Sorbitanesters can be obtained from ICI under the Tween® series of products.

In another embodiment of the invention, the non-reactive impactmodifiers can be synthesized in situ in the cellulose ester compositionby reacting cellulose ester-compatible compounds. These compounds canbe, for example, telechelic oligomers, which are defined as prepolymerscapable of entering into further polymerization or other reactionthrough their reactive end groups. In one embodiment of the invention,these in situ impact modifiers can have higher molecular weight (weightaverage molecular weight Mw) from about 10,000 to about 1,000,000.

In another embodiment of the invention, the impact modifier can bereactive. The reactive impact modifier can comprise a polymer oroligomer compatible with one component of the composition andfunctionality capable of reacting with another component of thecomposition. In embodiments, there are two types of reactive impactmodifiers that can be used. The first reactive impact modifier has ahydrocarbon chain that is compatible with the cellulose ester and alsohas functionality capable of reacting with the cellulose ester. Suchfunctional groups include, but are not limited to, carboxylic acids,anhydrides, acid chlorides, epoxides, and isocyanates. Specific examplesof this type of reactive impact modifier include, but are not limitedto: long chain fatty acids, such as, stearic acid (octadecanoic acid);long chain fatty acid chlorides, such as, stearoyl chloride(octadecanoyl chloride); long chain fatty acid anhydrides, such as,stearic anhydride (octadecanoic anhydride); epoxidized oils and fattyesters; styrene maleic anhydride copolymers; maleic anhydride graftedpolypropylene; copolymers of maleic anhydride with olefins and/oracrylic esters, e.g. terpolymers of ethylene, acrylic ester and maleicanhydride; and copolymers of glycidyl methacrylate with olefins and/oracrylic esters, e.g. terpolymers of ethylene, acrylic ester, andglycidyl methacrylate.

Reactive impact modifiers can be obtained as SMA® 3000 styrene maleicanhydride copolymer from Sartomer/Cray Valley, Eastman G-3015® maleicanhydride grafted polypropylene from Eastman Chemical Company, Epolene®E-43 maleic anhydride grafted polypropylene obtained from WestlakeChemical, Lotader® MAH 8200 random terpolymer of ethylene, acrylicester, and maleic anhydride obtained from Arkema, Lotader® GMA AX 8900random terpolymer of ethylene, acrylic ester, and glycidyl methacrylate,and Lotarder® GMA AX 8840 random terpolymer of ethylene, acrylic ester,and glycidyl methacrylate.

Modified polyolefin impact modifiers can be obtained as Lotader,Fusabond, Elvloy PTW, Lotryl, Elvaloy AC, InterLoy).

The second type of reactive impact modifier has a polar chain that iscompatible with the cellulose ester and also has functionality capableof reacting with the cellulose ester. Examples of these types ofreactive impact modifiers include cellulose esters or polyethyleneglycols with olefin or thiol functionality. Reactive polyethylene glycolimpact modifiers with olefin functionality include, but are not limitedto, polyethylene glycol allyl ether and polyethylene glycol acrylate. Anexample of a reactive polyethylene glycol impact modifier with thiolfunctionality includes polyethylene glycol thiol. An example of areactive cellulose ester impact modifier includes mercaptoacetatecellulose ester.

In embodiments of the invention, the amount of impact modifier in thecellulose ester composition can range from about 1 wt % to about 30 wt%, or from about 1 wt % to about 15 wt %, or from about 5 wt % to about10 wt %, or from about 10 wt % to about 30 wt %, or from about 15 wt %to about 30 wt %, based on the weight of the cellulose estercomposition.

In another embodiment of the invention, the cellulose ester compositionsfurther comprise at least one additional polymeric component as a blend(with the cellulose ester) in an amount from 5 to 95 weight %, based onthe total cellulose ester composition. Suitable examples of theadditional polymeric component include, but are not limited to, nylon;polyesters; polyamides; polystyrene; other cellulose esters, celluloseethers; polystyrene copolymers; styrene acrylonitrile copolymers;polyolephins; polyurethanes; acrylonitrile butadiene styrene copolymers;poly(methylmethacrylate); acrylic copolymers; poly(ether-imides);polyphenylene oxides; polyvinylchloride; polyphenylene sulfides;polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates;polysulfones; poly lactic add; poly butylenesuccinate; polysulfoneethers; and poly(ether-ketones) of aromatic dihydroxy compounds; ormixtures of any of the foregoing polymers. The blends can be prepared byconventional processing techniques known in the art, such as meltblending or solution blending.

In one embodiment of the invention, the composition can contain aplasticizer. The plasticizer utilized in this invention can be any thatis known in the art that can reduce the glass transition temperatureand/or the melt viscosity of the cellulose ester to improve meltprocessing characteristics. The plasticizer may be any plasticizersuitable for use with a cellulose ester. The plasticizer level should belower than the normal (or typical) plasticizer level for celluloseesters; so that the compositions have higher Tg (or HDT) than fullyplasticized cellulose ester compositions, good toughness and good flow.In embodiments, the plasticizer is present in an amount that does notsubstantially reduce the Tg (or HDT) of the cellulose ester compositioncompared to a similar composition without the plasticizer. Inembodiments, the Tg (or HDT) does not change (e.g., reduce) more than20%, or 15%, or 10%, or 5%, or 2%, as a result of including theplasticizer.

The plasticizer can be either monomeric or polymeric in structure. Inone embodiment, the plasticizer is at least one selected from the groupconsisting of an aromatic phosphate ester plasticizer, alkyl phosphateester plasticizer, dialkylether diester plasticizer, tricarboxylic esterplasticizer, polymeric polyester plasticizer, polyglycol diesterplasticizer, polyester resin plasticizer, aromatic diester plasticizer,aromatic trimester plasticizer, aliphatic diester plasticizer, carbonateplasticizer, epoxidized ester plasticizer, epoxidized oil plasticizer,benzoate plasticizer, polyol benzoate plasticizer adipate plasticizer, aphthalate plasticizer, a glycolic acid ester plasticizer, a citric acidester plasticizer, a hydroxyl-functional plasticizer, or a solid,non-crystalline resin plasticizer.

In one embodiment of the invention, the plasticizer can be selected fromat least one of the following: triphenyl phosphate, tricresyl phosphate,cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenylbiphenylphosphate, trioctyl phosphate, tri butyl phosphate, diethyl phthalate,dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate,dibenzyl phthalate, butyl phthalyl butyl glycolate, ethyl phthalyl ethylglycolate, methyl phthalyl ethyl glycolate, triethyl citrate,tri-n-butyl citrate, acetyltriethyl citrate, acetyl-tri-n-butyl citrate,and acetyl-tri-n-(2-ethylhexyl) citrate, diethylene glycol dibenzoate,dipropylene glycol dibenozoate, or triethylene glycol dibenzoate.

In another embodiment of the invention, the plasticizer can be selectedfrom at least one of the following: esters comprising: (i) acid residuescomprising one or more residues of: phthalic acid, adipic acid,trimellitic acid, succinic acid, benzoic acid, azelaic acid,terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citricacid or phosphoric acid; and (ii) alcohol residues comprising one ormore residues of an aliphatic, cycloaliphatic, or aromatic alcoholcontaining up to about 20 carbon atoms.

In another embodiment of the invention, the plasticizer can be selectedfrom at least one of the following: esters comprising: (i) at least oneacid residue selected from the group consisting of phthalic acid, adipicacid, trimellitic acid, succinic acid, benzoic acid, azelaic acid,terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citricacid and phosphoric acid; and (ii) at least one alcohol residue selectedfrom the group consisting of aliphatic, cycloaliphatic, and aromaticalcohol containing up to about 20 carbon atoms.

In another embodiment of the invention, the plasticizer can comprisealcohol residues where the alcohol residues is at least one selectedfrom the following: stearyl alcohol, lauryl alcohol, phenol, benzylalcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentylglycol, 1,4-cyclohexanedimethanol, and diethylene glycol.

In another embodiment of the invention, the plasticizer can be selectedfrom at least one of the following: benzoates, phthalates, phosphates,arylene-bis(diaryl phosphate), and isophthalates. In another embodiment,the plasticizer comprises diethylene glycol dibenzoate, abbreviatedherein as “DEGDB”.

In another embodiment of the invention, the plasticizer can be selectedfrom at least one of the following: aliphatic polyesters comprisingC₂₋₁₀ diacid residues, for example, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,and sebacic acid; and C₂₋₁₀ diol residues.

In another embodiment, the plasticizer can comprise diol residues whichcan be residues of at least one of the following C₂-C₁₀ diols: ethyleneglycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentylglycol, 1,5-pentanediol, 1,6 hexanediol, 1,5-pentylene glycol,triethylene glycol, and tetraethylene glycol.

In another embodiment of the invention, the plasticizer can includepolyglycols, such as, for example, polyethylene glycol, polypropyleneglycol, and polybutylene glycol. These can range from low molecularweight dimers and trimers to high molecular weight oligomers andpolymers. In one embodiment, the molecular weight of the polyglycol canrange from about 200 to about 2000.

In another embodiment of the invention, the plasticizer comprises atleast one of the following: Resoflex® R296 plasticizer, Resoflex® 804plastocizer, SHP (sorbitol hexapropionate), XPP(xylitolpentapropionate), XPA(xylitol pentaacetate), GPP(glucose pentaacetate),GPA (glucose pentapropionate) and APP (arabitol pentapropionate).

In another embodiment of the invention, the plasticizer comprises one ormore of: A) from about 5 to about 95 weight % of a C₂-C₁₂ carbohydrateorganic ester, wherein the carbohydrate comprises from about 1 to about3 monosaccharide units; and B) from about 5 to about 95 weight % of aC₂-C₁₂ polyol ester, wherein the polyol is derived from a C₅ or C₆carbohydrate. In one embodiment, the polyol ester does not comprise orcontain a polyol acetate or polyol acetates.

In another embodiment, the plasticizer comprises at least onecarbohydrate ester and the carbohydrate portion of the carbohydrateester is derived from one or more compounds selected from the groupconsisting of glucose, galactose, mannose, xylose, arabinose, lactose,fructose, sorbose, sucrose, cellobiose, cellotriose and raffinose.

In another embodiment of the invention, the plasticizer comprises atleast one carbohydrate ester and the carbohydrate portion of thecarbohydrate ester comprises one or more of α-glucose pentaacetate,β-glucose pentaacetate, α-glucose pentapropionate, β-glucosepentapropionate, α-glucose pentabutyrate and β-glucose pentabutyrate.

In another embodiment, the plasticizer comprises at least onecarbohydrate ester and the carbohydrate portion of the carbohydrateester comprises an α-anomer, a β-anomer or a mixture thereof.

In another embodiment, the plasticizer can be selected from at least oneof the following: propylene glycol dibenzoate, glyceryl tribenzoate,diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

In another embodiment of the invention, the plasticizer can be a solid,non-crystalline resin. These resins can contain some amount of aromaticor polar functionality and can lower the melt viscosity of the celluloseesters. In one embodiment of the invention, the plasticizer can be asolid, non-crystalline compound (resin), such as, for example, rosin;hydrogenated rosin; stabilized rosin, and their monofunctional alcoholesters or polyol esters; a modified rosin including, but not limited to,maleic- and phenol-modified rosins and their esters; terpene resins;phenol-modified terpene resins; coumarin-indene resins; phenolic resins;alkylphenol-acetylene resins; and phenol-formaldehyde resins.

In another embodiment of the invention, the plasticizer is at least oneplasticizer selected from the group consisting of: triacetin, trimethylphosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate,triethyl citrate, acetyl trimethyl citrate, acetyl triethyl citrate,acetyl tributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate,diaryl phthalate, diethyl phthalate, dimethyl phthalate,di-2-methoxyethyl phthalate, di-octyl phthalate, di-octyl adipate,dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalyl ethylglycolate, methyl phthalyl ethyl glycolate, n-ethyltoluenesulfonamide,o-cresyl β-toluenesulfonate, aromatic diol, substituted aromatic diols,aromatic ethers, tripropionin, tribenzoin, polycaprolactone, glycerin,glycerin esters, diacetin, glycerol acetate benzoate, polyethyleneglycol, polyethylene glycol esters, polyethylene glycol diesters,di-2-ethylhexyl polyethylene glycol ester, triethylene glycolbis-2-ethyl hexanoate, glycerol esters, diethylene glycol, polypropyleneglycol, polyglycoldiglycidyl ethers, dimethyl sulfoxide, N-methylpyrollidinone, C₁-C₂₀ dicarboxylic acid esters, dimethyl adipate,di-butyl maleate, di-octyl maleate, resorcinol monoacetate, catechol,catechol esters, phenols, epoxidized soy bean oil, castor oil, linseedoil, epoxidized linseed oil, other vegetable oils, other seed oils,difunctional glycidyl ether based on polyethylene glycol,γ-valerolactone, alkylphosphate esters, aryl phosphate esters,phospholipids, eugenol, cinnamyl alcohol, camphor, methoxy hydroxyacetophenone, vanillin, ethylvanillin, 2-phenoxyethanol, glycol ethers,glycol esters, glycol ester ethers, polyglycol ethers, polyglycolesters, ethylene glycol ethers, propylene glycol ethers, ethylene glycolesters, propylene glycol esters, polypropylene glycol esters,acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoicacid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate,ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, diethylene glycoldibenzoate, dipropylene glycol dibenozoate, triethylene glycoldibenzoate, butylated hydroxytoluene, butylated hydroxyanisol, sorbitol,xylitol, ethylene diamine, piperidine, piperazine, hexamethylenediamine, triazine, triazole, pyrrole, and any combination thereof.

The amount of plasticizer in the cellulose ester composition can rangefrom 0 to about 15 weight percent based on the weight of the celluloseester composition. In one embodiment, the amount can range up to about15 weight percent based on the weight of the cellulose estercomposition. In another embodiment, the amount can range up to about 10weight percent based on the weight of the cellulose ester composition.In another embodiment, the amount can range up to about 5 weight percentbased on the weight of the cellulose ester composition, or up to about 3weight percent based on the weight of the cellulose ester composition,or less than 2 weight percent based on the weight of the cellulose estercomposition.

In another embodiment of the invention, the composition contains noplasticizer. In one embodiment, the cellulose ester compositioncomprises a cellulose ester that is CAP and no plasticizer. In oneembodiment, the cellulose ester composition comprises a cellulose esterthat is CAB and no plasticizer.

In another embodiment of the invention, the composition is meltprocessable. Melt processability generally refers to the ability tothermally process the materials below their degradation temperature toobtain homogeneous pellets or plastic articles. For example, thecompositions described can be melt extruded on a Werner & Pflerderer 30mm twin screw extruder at a throughput of 35 lbs/hour with screw speedof 250 rpm and barrel temperature of 240° C. injection molded on a Toyo110 injection molding machine with barrel temperature of 240° C. andmold temperature of 160° F. with minimal molecular weight or colordegradation.

In one embodiment of this invention, a melt processable cellulose estercomposition is provided comprising 1 to 30 wt %, or 1 to 15 wt %, or 2to 10 wt % of impact modifiers and no plasticizer, the cellulose estercomposition having a heat deflection temperature (HDT) value of greaterthan 95° C. (measured according to ASTM D648 at a 1.82 MPa stress levelafter conditioning for 4 hours at 70° C.), and notched Izod impactstrength value of greater than 80 J/m (measured according to ASTM D256on 3.2 mm thick bars at 23° C.), and spiral flow values of at least 15inches at 240 C when measured using the procedure described herein. Inone embodiment, the cellulose ester composition has a Tg value measuredat 20 C/min according to ASTM D3418 of greater than 120° C.

In another embodiment of the invention, the compositions have a meltviscosity at 240° C. and 400 rad/s of 10,000 1/s or below measured by aplate-plate melt rheometer such as aRheometrics Dynamic Analyzer (RDAII) with 25 mm diameter parallel plates, 1 mm gap and 10% strainmeasured in accordance with ASTM D4440 using frequency scan of between 1rad/sec and 400 rad/sec.

In one embodiment, the melt processable cellulose ester compositionscomprise 0 to 30 wt %, or 0 to 15 wt % of impact modifiers, 0 to 15 wt %of plasticizers, and have a Tg greater than 90° C. In anotherembodiment, the melt processable cellulose ester compositions comprise 0to 30 wt %, or 0 to 15 wt % of impact modifiers, 0 to 10 wt % ofplasticizers, and have a Tg greater than 100° C. In yet anotherembodiment, melt processable cellulose ester compositions comprise 0 to10 wt % of impact modifiers, 0 to 10 wt % of plasticizers, and have a Tggreater than 100° C. In another embodiment, melt processable celluloseester compositions comprise 0 to 10 wt % of impact modifiers, 0 to 5 wt% of plasticizers, and have a Tg greater than 115° C.

In another embodiment of the invention, the cellulose ester compositionshave a Tg or Heat deflection temperature (HDT at 0.455 psi) similar tothat of the base cellulose ester polymer with a drop of only a fewdegrees Celsius (e.g., less than 5° C., or less than 2° C.) with theincorporation of an impact modifier and no plasticizer. Impactproperties of these composition can also exceed 80 J/m (notched Izodimpact strength at 23° C.).

In embodiments of the invention, the polymer-based resin has a heatdistortion temperature (“HDT”) greater than 90° C., or greater than 95°C., according to ASTM D648 as measured at 1.82 MPa using a 3.2 mm thickbar that was subjected to 70° C. for 4 hours. In certain embodiments,the polymer-based resin has a heat distortion temperature (“HDT”) of atleast 95° C., at least 100° C., at least 105° C., or at least 110° C.,or at least 115° C. In certain embodiments, the polymer-based resin hasa heat distortion temperature (“HDT”) in the range from 90° C. to 140°C., 90° C. to 130° C., 90° C. to 120° C., 90° C. to 110° C., 95° C. to140° C., 95° C. to 130° C., 95° C. to 120° C., 95° C. to 110° C., 95° C.to 105° C., 100° C. to 140° C., 100° C. to 130° C., 100° C. to 120° C.,100° C. to 110° C., 105° C. to 140° C., 105° C. to 130° C., 105° C. to120° C., 105° C. to 115° C., 105° C. to 110° C., 110° C. to 140° C.,110° C. to 130° C., 110° C. to 125° C., 110° C. to 120° C., 110° C. to115° C., 115° C. to 140° C., 115° C. to 130° C., 120° C. to 140° C.,120° C. to 130° C., or 120° C. to 125° C.

In embodiments of the invention, the polymer-based resin has a notchedizod impact strength of at least 80 J/m, or at least 90 J/m, or at least100 J/m, or at least 110 J/m, or at least 120 J/m, or at least 130 J/m,or at least 140 J/m, or at least 150 J/m, or at least 160 J/m, or atleast 170 J/m, or at least 180 J/m, or at least 190 J/m, or at least 200J/m, as measured according to ASTM D256 using a 3.2 mm thick bar thathas been subjected to 50% relative humidity for 48 hours at 23° C. Incertain embodiments, the polymer-based resin has a notched izod impactstrength in the range of from about 80 J/m to about 500 J/m, from about80 J/m to about 400 J/m, from about 80 J/m to about 300 J/m, from about80 J/m to about 200 J/m, from about 100 J/m to about 500 J/m, from about100 J/m to about 400 J/m, from about 100 J/m to about 300 J/m, fromabout 100 J/m to about 200 J/m, from about 120 J/m to about 500 J/m,from about 120 J/m to about 400 J/m, from about 120 J/m to about 300J/m, from about 120 J/m to about 200 J/m, from about 150 J/m to about500 J/m, from about 150 J/m to about 400 J/m, from about 150 J/m toabout 300 J/m, from about 150 J/m to about 200 J/m, from about 170 J/mto about 500 J/m, from about 170 J/m to about 400 J/m, from about 170J/m to about 300 J/m, from about 170 J/m to about 200 J/m, from 180 J/mto about 500 J/m, from about 180 J/m to about 400 J/m, from about 180J/m to about 300 J/m, from about 180 J/m to about 200 J/m, from 190 J/mto about 500 J/m, from about 190 J/m to about 400 J/m, from about 190J/m to about 300 J/m, from about 190 J/m to about 200 J/m, from 200 J/mto about 500 J/m, from about 200 J/m to about 400 J/m, or from about 200J/m to about 300 J/m, as measured according to ASTM D256 using a 3.2 mmthick bar that has been subjected to 50% relative humidity for 48 hoursat 23° C.

In another embodiment of the invention, the cellulose ester compositionsfurther comprise at least one additive selected from the groupcomprising antioxidants, thermal stabilizers, mold release agents,antistatic agents, whitening agents, colorants, flow aids, processingaids, plasticizers, anti-fog additives, minerals, UV stabilizers,lubricants, chain extenders, nucleating agents, reinforcing fillers,wood or flour fillers, glass fiber, carbon fiber, flame retardants,dyes, pigments, colorants, additional resins and combinations thereof.

In embodiments, mixing of the impact modifiers, cellulose esters, andthe optional plasticizers and any additives can be accomplished by anymethod known in the art that is adequate to disperse the impactmodifiers, plasticizers and additives into the cellulose esters.Examples of mixing equipment include, but are not limited to, Banburymixers, Brabender mixers, roll mills, and extruders (single or twinscrew). The shear energy during the mixing is dependent on thecombination of equipment, blade design, rotation speed (rpm), and mixingtime. The shear energy should be sufficient to disperse the impactmodifier throughout the cellulose ester.

In embodiments, the cellulose ester, impact modifier, plasticizer andadditives can be combined in any order during the process. In oneembodiment, the cellulose ester is premixed with the impact modifierand/or the plasticizer. The cellulose ester containing the impactmodifier and/or the plasticizer is then mixed with the additives. Inanother embodiment of the invention, when reactive impact modifiers areutilized, the reactive impact modifiers can be mixed with the celluloseesters first, and then the other components are added.

In certain embodiments of the invention, the cellulose estercompositions contain 2 wt %-15 wt % impact modifier, based on the totalweight of the cellulose ester composition, and have HDT values greaterthan 95 C, and notched Izod impact strength values greater than 80 J/m,and viscosities at 240 C and 400 rad/sec greater than 10,000 P.

In another embodiment, cellulose ester compositions are provided thathave a total DS/AGU in the range from about 2 to about 2.99 and theDS/AGU of acetyl ranges from about 0 to about 2.2, with the remainder ofthe ester groups comprising propionyl, butyryl or combinations thereof.

In other embodiments, the melt processable cellulose ester compositionsdescribed above, optionally contain some plasticizer. In embodiments,the plasticizer is present in an amount that does not substantiallyreduce the HDT of the cellulose ester composition compared to a similarcomposition without the plasticizer. In embodiments, the HDT does notchange (e.g., reduce) more than 10%, or 5%, or 2%, as a result ofincluding the plasticizer.

In one aspect, the invention is directed to an injection molded articlecomprising a thin-walled body portion formed from a polymer-based resinderived from cellulose,

wherein the thin-walled body portion comprises:

-   -   i. a gate position;    -   ii. a last fill position;    -   iii. a flow length to wall thickness ratio greater than or equal        to 100, wherein the flow length is measured from the gate        position to the last fill position; and    -   iv. a wall thickness less than or equal to about 2 mm; and

wherein the polymer-based resin has an HDT or at least 90 C, or at least95 C, a bio-derived content of at least 20 wt %, or at least 40 wt %,and a spiral flow length of at least 3.0 cm, when the polymer-basedresin is molded with a spiral flow mold with the conditions of a barreltemperature of 238° C., a melt temperature of 246° C., a moldingpressure of 13.8 MPa, a mold thickness of 0.8 mm, and a mold width of12.7 mm. In embodiments, the polymer-based resin has a spiral flowlength of at least 4.0, or at least 5.0 cm.

In one embodiment of the injection molded article, the polymer-basedresin further comprises at least one property chosen from: flexuralmodulus of greater than 1900 MPa as measured according to ASTM D790using a 3.2 mm thick bar hat has been subjected to 50% relative humidityfor 48 hours at 23° C.; a notched izod impact strength of greater than80 J/m as measured according to ASTM D256 using a 3.2 mm thick bar hathas been subjected to 50% relative humidity for 48 hours at 23° C.; aflex creep deflection of less than 12 mm, measured using a molded barhaving dimensions of 5″ length, 0.5″ width, and 0.125″ thicknesspositioned horizontally on a fixture with a 4″ span, inside a dry ovenfor 68 hours at 90° C. with a nominal 500 psi stress on the center ofthe span; a transmission of at least 70 measured according to ASTM D1003using a 3.2 mm plaque after injection molding at a barrel set point of249° C. and a residence time of 5 min; a ΔE value of less than 25, usinga 3.2 mm plaque after injection molding with a barrel temperature of249° C. and a residence time of 5 min; or an L* color of at least 85,measured according to ASTM E1348 using a 3.2 mm plaque after injectionmolding with a barrel temperature of 249° C. and a residence time of 5min. In embodiments, the polymer-based resin comprises at least 2, or atleast 3 of the listed properties. In embodiments, the polymer-basedresin contains less than 5 wt %, or less than 4 wt %, or less than 3 wt%, or less than 2 wt %, or less than 1 wt %, or has no addedplasticizer.

By “wall thickness” is meant the average wall thickness of thethin-walled body portion, unless specified otherwise. In one embodiment,the wall thickness can be the average wall thickness of the entiremolded article. In one embodiment, the wall thickness is substantiallyconstant.

The “gate position” is the point where the gate is located where theinjection molding polymer enters the mold during the injection moldingprocess. Various types of gates can be employed for preparing moldedarticles, such as for example, side gates, spoke gates, pin gates,submarine gates, film gates, disk gates, or any combination thereof.

The “last fill position” is the location in the mold cavity furthestfrom the gate position, where polymer is intended to fill duringinjection molding.

The “gate size” is the diameter of the gate opening, when it is acircular gate. For non-circular gate openings, it is the effectivediameter, or smallest dimension of the opening.

In embodiments, the gate position comprises a gate having a gate size,wherein ratio of gate size to wall thickness is 1:1 or less, or 0.9:1 orless, 0.8:1 or less, or 0.7:1 or less, or 0.6:1 or less, or 0.5:1 orless. In embodiments, the gate position comprises a gate having a gatesize, wherein ratio of gate size to wall thickness is in the range from1:1 to 0.1:1, or 0.9:1 to 0.1:1, or 0.8:1 to 0.1:1, or 0.7:1 to 0.1:1,or 0.6:1 to 0.1:1, or 0.5:1 to 0.1:1.

In embodiments, the gate size is 1.0 mm or less, or 0.9 mm or less, 0.8mm or less, or 0.7 mm or less, 0.6 mm or less, or 0.5 mm or less. Inembodiments, the wall thickness is 1.9 mm or less, or 1.8 mm or less,1.7 mm or less, or 1.6 mm or less, 1.5 mm or less, or 1.4 mm or less, or1.3 mm or less, 1.2 mm or less, or 1.1 mm or less, 1.0 mm or less, or0.9 mm or less, 0.8 mm or less, or 0.7 mm or less, 0.6 mm or less, or0.5 mm or less.

In certain embodiments, the flow length to wall thickness ratio is atleast 100, or at least 150, or at least 200, or at least 250, or atleast 300, or at least 350, or at least 400, or at least 450, or atleast 500, wherein the flow length is measured from the gate position tothe last fill position. In certain embodiments, the flow length to wallthickness ratio is in the range from 100 to 1500, or from 100 to 1250,or from 100 to 1000, or from 100 to 750, or from 150 to 1500, or from150 to 1250, or from 150 to 1000, or from 150 to 750, or from 200 to1500, or from 200 to 1250, or from 200 to 1000, or from 200 to 750, orfrom 250 to 1500, or from 250 to 1250, or from 250 to 1000, or from 250to 750, or from 300 to 1500, or from 300 to 1250, or from 300 to 1000,or from 300 to 750, or from 350 to 1500, or from 350 to 1250, or from350 to 1000, or from 350 to 750, or from 400 to 1500, or from 400 to1250, or from 400 to 1000, or from 400 to 750, or from 450 to 1500, orfrom 450 to 1250, or from 450 to 1000, or from 450 to 750, or from 500to 1500, or from 500 to 1250, or from 500 to 1000, or from 500 to 750,wherein the flow length is measured from the gate position to the lastfill position.

In embodiments of the invention, the molded article has a flow length towall thickness ratio in excess of 450 with wall thicknesses of less thanabout 1.0 millimeter, such as ratios from about 450 to about 1500;ratios in excess of about 350 with wall thicknesses of less than about0.75 millimeter, such as ratios from about 350 to about 1250; ratios inexcess of about 200 with wall thicknesses of less than about 0.5millimeter, such as ratios from about 300 to about 1000; ratios inexcess of about 200 with wall thicknesses of less than about 1millimeter, such as ratios from about 200 to about 1000; ratios inexcess of about 200 with wall thicknesses of less than about 0.375millimeter, such as ratios from about 250 to about 750; and ratios inexcess of about 150 with wall thicknesses of less than about 0.25millimeter, such as ratios from about 150 to about 500.

In embodiments, the polymer-based resin forming the injection moldedarticle is chosen from any of the cellulose ester compositions discussedherein. In one embodiment, the resin is a cellulose ester compositioncomprising CAP, a secondary antioxidant, and an acid scavenger, andhaving an HOT greater than 95° C. In one embodiment, this celluloseester composition further comprises 1 to 30 wt % of an impact modifier,less than 2 wt % of a plasticizer, or no plasticizer, and less than 5 wt%, or less than 2 wt % of any other additives.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLES

This invention can be further illustrated by the following examples ofembodiments thereof. These examples are included merely for purposes ofillustration and are not intended to limit the scope of the inventionunless otherwise specifically indicated.

Abbreviations

Ex is example(s); CA is cellulose acetate; CAB is cellulose acetatebutyrate; CAP is cellulose acetate propionate; % H is percent haze; % Tis percent transmission; M_(w) is absolute weight average molecularweight, ΔM_(w)% is change in absolute weight average molecular weight; %H is percent haze; RH is relative humidity; ° C. is Degree(s) Celsius;min is minute(s); ° F. is Degree(s) Fahrenheit; Comp. Ex. is comparativeexample; Pz is plasticizer; Antiox. is antioxidant; SNMO is AKCROSTABSN-MO; Temp. is temperature; min is minute; NPPP is WESTONNeopentylphenylphosphite; Prim. Is primary; IM is impact modifier; Scav.is scavenger; Stab. Is stabilizer; CE is cellulose ester; oz is ounce;in/sec is inch/second; sec or s is second(s); psi is pounds per squareinch; BSP is barrel set point; RT is residence time.

General Procedure for Preparation of Compositions

The examples were prepared by pre-mixing the cellulose ester powder withadditives such as stabilizers, impact modifiers and plasticizers at roomtemperature for 20 minutes in a Hobart mixer.

Example 1

Example 1 was prepared by mixing Eastman™ CAP 482-20 (18.484 lb, 92.42wt %), ECO 100 (1.2 lb, 6.0 wt %), IRGANOX 1010 (0.05 lb, 0.25 wt %),IRGAFOS 168 (0.066 lb, 0.33 wt %), DRAPEX 4.4 (0.194 lb, 0.97 wt %),SNMO (0.0006 lb, 0.03 wt %) in a Hobart mixer for 20 minutes at roomtemperature.

A series of compositions were made to determine the effect of differentstabilizers on critical properties as noted in the examples in Table 1.The base material used for these examples was Eastman™ CAP 482-20.

TABLE 1 Ex. 2-13 Prim. Second. Acid Salt CE, IM, Antiox., Antiox.,Scav., Stab., EX # Wt % (Wt %) (Wt %) (Wt %) (Wt %) (Wt %) 2 CAP 482-20NPPP DRAPEX 4.4 SNMO (98.98) (0.10) (0.90) (0.02) 3 CAP 482-20 ECO100NPPP DRAPEX 4.4 SNMO (92.98) (6.0) (0.10) (0.90) (0.02) 4 CAP 482-20ECO100 ULTRANOX 626 DRAPEX 4.4 SNMO (92.97) (6.0)   (0.33%) (0.68)(0.02) 5 CAP 482-20 ULTRANOX 626 DRAPEX 4.4 SNMO (98.97) (0.33) (0.68)(0.02) 6 CAP 482-20 ECO100 IRGANOX 1010 ULTRANOX 626 DRAPEX 4.4 SNMO(92.72) (6.0) (0.25) (0.33) (0.68) (0.02) 7 CAP 482-20 ECO100 IRGANOX1010 ULTRANOX 626 DRAPEX 4.4 SNMO (92.47) (6.0) (0.50) (0.33) (0.68)(0.02) 8 CAP 482-20 ECO100 IRGANOX 1010 ULTRANOX 626 DRAPEX 4.4 SNMO(92.42) (6.0) (0.25) (0.33) (0.97)   (0.03%) 9 CAP 482-20 ECO100 IRGANOX1010 ULTRANOX 626 DRAPEX 4.4 SNMO (92.72) (6.0) (0.25) (0.33) (0.68)(0.02) 10 CAP 482-20 ECO100 IRGANOX 1010 ULTRANOX 626 VIKOFLEX 7170 SNMO(92.42)   (6.0%) (0.25) (0.33) (0.97) (0.03) 11 CAP 482-20 ECO100IRGANOX 1010 ULTRANOX 626 VIKOFLEX 7170 SNMO (92.17)   (6.0%) (0.50)(0.33) (0.97) (0.03) 12 CAP 482-20 IRGANOX 1010 ULTRANOX 626 DRAPEX 4.4SNMO (98.17) (0.50) (0.33) (0.97) (0.03) 13 CAP 482-20 ECO100 IRGANOX1010 ULTRANOX 626 DRAPEX 4.4 SNMO (92.17) (6.0) (0.50) (0.33) (0.97)(0.03)

Comp. Ex. 1 is a control and is a typical Plasticized CE formulationmade from CAP 482-20, and is comparative due to low HDT. Comp. Ex. 2 wasprepared by adapting the previously disclosed procedures, and iscomparative for embodiments of the invention requiring low ΔE and/orhigh transmission. The base material used for these comparative exampleswas Eastman™ CAP 482-20.

TABLE 2 Comp. Ex. 1-4 Prim. Second. Acid Salt CE, Pz, IM, Antiox.,Antiox., Scav., Stab., Comp. EX # (Wt %) (Wt %) (Wt %) (Wt %) (Wt %) (Wt%) (Wt %) 1 CAP 482-20 DOA NPPP DRAPEX 4.4 SNMO (93.0)  (6.0) (0.10)(0.8) (0.02) 2 CAP 482-20 ECO100 IRGANOX 1010 DRAPEX 4.4 SNMO  (92.17)(6.0)   (0.50%)/  (0.97) (0.03) LOWINOX 44B25 (0.33) 3 CAP 482-20 DOANPPP DRAPEX 4.4 SNMO (88.0) (11.1) (0.09) (0.8) (0.02) 4 CA 398-30 DEPt-Butyl Phenol NPPP DRAPEX 4.4 SNMO (73.0) (26.2) (0.29) (0.05) (0.4)(0.01)

Pellet Production

The premixed material (Ex 1-13 and Comp. Ex. 1-4) was then fed into thethroat of a Davis-Standard 32 mm extruder and compounded at a throughputof 40 lb/hour with screw speed of 300 rpm and barrel temperature of 225°C. for the Eastman™ CAP 482-20 based compositions to produce pellets.

Plaque Production

Pellets of the compounded material were injection molded in a 150 TonToyo injection molding machine with a barrel capacity of 6.7 oz at 1in/sec injection speed into two 4 inch×4 inch×0.126 (10.2 cm×10.2cm×0.32 cm) plaques per shot with barrel temperature nominally of 249°C. (480° F.) or 260° C. (500° F.) with a residence time of 2 min or 5min, and a mold temperature of 80° C.

Test Bar Production

Pellets of the compounded material were injection molded to formstandard test bars 0.5 inch×5 inch×0.125 inch (1.27 cm×12.7 cm×0.3 cm).The pellets were molded in A 110 Ton Toyo injection molding machine withbarrel capacity 3.4 oz. The compounded material is typically injectionmolded at 1 in/sec injection speed into four test bars per shot withbarrel temperature nominally of 249° C. (480° F.) and mold temperatureof 80° C.

Test Methods

Samples were evaluated using standard ASTM test methods with any specialconditions noted below.

TABLE 3 Test Methods PROPERTY COMMENTS Color, b* (ASTM E1348) Using 3.2mm thick plaques. Measured using Hunter Lab Ultrascan SpectraColorimeter Color, a* (ASTM E1348) Using 3.2 mm thick plaques. Measuredusing Hunter Lab Ultrascan Spectra Colorimeter Color, L* (ASTM E1348)Using 3.2 mm thick plaques. Measured using Hunter Lab Ultrascan SpectraColorimeter Haze (ASTM D1003) Using 3.2 mm plaques Transmission Using3.2 mm plaques (ASTM D1003) Δ M_(w) % (GPC) % Change in Absolute WeightAverage Molecular Weight From Pellet To Plaque or Test Bar Based OnPellet Absolute Molecular Weight Izod Notched Impact Using a 0.32 mmthick bar that has been at 23° C. subjected to 50% relative humidity(ASTM D256) at 23° C. for 48 hours. HDT 1.82 MPa Using a 0.32 mm thickbar subjected to (ASTM D648) 70° C. for 4 hours. Flexural Modulus Usinga 1.3 cm × 12.7 cm × 0.3 mm bar (ASTM D790) subjected to 50% Relativehumidity for 48 hours at 23° C. Absolute Weight Average Usingtetrahydrofuran stabilized with BHT Molecular Weight as a solvent and aflow rate of 1 mL/min. (ASTM D5296)

Spiral Flow

3.2 mm Thick Bar

A reciprocating screw injection molding machine having 110 tons ofclamping force with a screw diameter of 32 mm was equipped with awater-cooled, cold runner mold with a spiral-shaped cavity havingdimensions of 0.50″ wide×0.125″ deep×60.00″ in length. The cavity wasfed via a 3.5″ long cold sprue with a nominal 0.400″ diameter and3-degree taper, followed by a 1.0″ long cold runner with 0.30″ nominaldiameter, followed by a rectangular gate 0.25″ wide×0.050″ thick×0.10″long. Variables controlled for the range of experimentation includedresin drying, injection unit barrel temperature, mold temperature,initial injection speed, injection pressure limit, screw rotation speedand back pressure on screw recovery, injection time, and cycle time.

For each combination of variables, responses included actual melttemperature and distance of melt travel in the spiral-shaped cavity,excluding the runner and gate. The injection process was allowed tostabilize at each set of conditions—typically 10 to 15 shots—and then 10molded specimens were collected for an average reported flow length.

All materials were molded using pressure control, with mold temperatureof 80 F, initial injection speed of 1 in/s, injection unit pressurelimit of 1000 psi, injection time of 10 s, cycle time of 38 s, maximumcushion of 0.1″, screw recovery rotation speed of 150 rpm, and screwrecovery back pressure of 100 psi.

0.8 mm Thick Bar

A reciprocating screw injection molding machine having 110 tons ofclamping force with a screw diameter of 32 mm was equipped with awater-cooled, cold runner mold with a spiral-shaped cavity havingdimensions of 0.50″ wide×0.030″ deep×60.00″ in length. The cavity wasfed via a 3.5″ long cold sprue with a nominal 0.400″ diameter and3-degree taper, followed by a 1.0″ long cold runner with 0.30″ nominaldiameter, followed by a rectangular gate 0.25″ wide×0.030″ thick×0.10″long. Variables controlled for the range of experimentation includedresin drying, injection unit barrel temperature, mold temperature,initial injection speed, injection pressure limit, screw rotation speedand back pressure on screw recovery, injection time, and cycle time.

For each combination of variables, responses included actual melttemperature and distance of melt travel in the spiral-shaped cavity,excluding the runner and gate. The injection process was allowed tostabilize at each set of conditions—typically 10 to 15 shots—and then 10molded specimens were collected for an average reported flow length.

All materials were molded using pressure control, with mold temperatureof 120° F. (49° C.), initial injection speed of 1 in/s, injection unitpressure limit of 2000 psi, injection time of 5 s, cycle time of 32 s,maximum cushion of 0.2″, screw recovery rotation speed of 150 rpm, andscrew recovery back pressure of 100 psi.

Test Results

The following results in Table 4 (Ex. 1-13 and Comp. Ex. 2-4) wereobtained using 4 inch×4 inch plaques which were molded from pellets ofcompounded materials. The injection molding conditions are provided, andthe color (L*, a*, b*), % H, and % T of the resulting plaques. The M_(w)of the cellulose ester at the pellet stage and after being molded at theplaque stage are provided along with the % ΔM_(w) (from pellet toplaque).

TABLE 4 Analytical Results Injection Molding Conditions Analytical DataRT % % Plaque Pellet Δ M_(W), EX#. BSP ° F. min Color L* Colora* Colorb* ΔE H T M_(W) M_(W) % 1-1 480 2 90.1 −0.4 16.8 5.6 80 120,068 117,302−2 1-2 480 5 86.5 0.3 25.8 29.1 5.4 73 116,153 117,302 1 1-3 500 2 88.6−0.1 20.4 5.8 77 116,394 117,302 1 1-4 500 5 79.9 3.0 38.6 5.8 61110,084 117,302 6 2-1 480 2 94.0 −0.9 7.6 4.8 87 102,309 110,791 8 2-2480 5 93.5 −1.3 10.4 12.3 4.4 86 101,465 110,791 8 2-3 500 2 93.9 −1.18.9 3.9 87 92,971 110,791 16 2-4 500 5 92.9 −1.5 12.0 3.8 85 91,000110,791 18 3-1 480 2 91.3 −0.5 11.1 10.8 82 113,730 122,000 7 3-2 480 590.0 −0.9 13.2 20.0 9.1 80 108,112 122,000 11 3-3 500 2 91.2 −0.5 11.511.6 82 112,114 122,000 8 3-4 500 5 88.5 −0.7 22.2 11.2 77 104,552122,000 14 4-1 480 2 92.2 −0.6 8.5 10.1 83 97,790 112,990 13 4-2 480 591.9 −0.8 10.2 13.0 10.2 83 97,381 112,990 14 4-3 500 2 92.1 −0.6 9.38.6 84 94,034 112,990 17 4-4 500 2 91.3 −1.5 14.8 9.1 82 83,678 112,99026 5-1 480 2 95.4 −1.0 6.2 3.5 90 101,156 110,791 9 5-2 480 5 95.2 −1.37.6 9.1 3.3 90 97,851 110,791 12 5-3 500 2 95.1 −1.1 6.8 3.9 89 97,808110,791 12 5-4 500 5 94.7 −1.7 9.8 4.3 89 95,017 110,791 14 6-1 480 292.8 −0.5 8.0 8.2 85 103,918 119,568 13 6-2 480 5 92.4 −1.0 10.4 12.98.4 84 94,343 119,568 21 6-3 500 2 92.6 −0.7 9.0 8.1 85 101,442 119,56815 6-4 500 5 91.8 −1.6 14.5 9.0 83 90,128 119,568 25 7-1 480 2 93.3 −0.67.4 7.4 86 100,031 122,041 18 7-2 480 5 92.9 −1.0 9.8 12.1 7.6 85 88,293122,041 28 7-3 500 2 93.1 −0.7 8.3 8.0 86 95,918 122,041 21 7-4 500 592.1 −1.8 14.6 9.2 84 79,172 122,041 35 8-1 480 2 92.3 −0.5 8.1 8.6 84103,009 116,085 11 8-2 480 5 91.7 −0.8 10.0 13.0 9.9 83 91,906 116,08521 8-3 500 2 92.0 −0.6 9.0 9.0 84 102,082 116,085 12 8-4 500 5 91.5 −1.713.9 10.9 82 72,366 116,085 38 9-1 480 2 92.6 −0.5 8.2 8.8 84 108,968108,737 0 9-2 480 5 92.3 −0.8 10.3 12.9 8.7 84 101,302 108,737 7 9-3 5002 92.4 −0.6 9.1 9.2 84 105,879 108,737 3 9-4 500 5 91.5 −1.4 14.3 9.6 8292,335 108,737 15 10-1  480 2 93.0 −0.6 8.2 8.9 85 113,322 107,580 −510-2  480 5 92.2 −0.9 10.9 13.5 13.9 84 111,361 107,580 −4 10-3  500 292.3 −0.8 9.8 16.7 84 109,350 107,580 −2 10-4  500 5 91.8 −1.4 14.1 12.683 109,292 107,580 −2 11-1  480 2 93.6 −0.8 8.7 6.9 87 116,249 121,487 411-2  480 5 93.2 −1.1 11.0 13.0 7.0 86 118,493 121,487 2 11-3  500 293.3 −0.9 9.8 7.3 86 117,424 121,487 3 11-4  500 5 92.0 −1.6 15.8 8.2 84112,515 121,487 7 12-1  480 2 95.1 −0.9 6.5 4.0 89 102,722 109,000 612-2  480 5 94.9 −1.2 8.3 9.9 3.8 89 101,143 109,000 7 12-3  500 2 94.8−1.1 7.9 4.0 89 97,531 109,000 11 12-4  500 5 94.0 −1.9 12.8 3.9 8798,119 109,000 10 13-1  480 2 92.3 −0.5 8.0 9.9 84 102,109 110,000 713-2  480 5 91.9 −1.1 11.1 13.8 8.5 83 98,500 110,000 10 13-3  500 292.3 −0.7 8.5 10.5 84 102,278 110,000 7 13-4  500 5 91.8 −1.4 12.6 10.883 88,676 110,000 19 Comp Ex 480 2 89.1 −0.2 18.0 6.9 77 115,272 126,4559 2-1 Comp Ex 480 5 85.6 0.6 26.8 30.5 6.6 72 112,983 126,455 11 2-2Comp Ex 500 2 87.2 0.2 22.5 7.2 75 113,373 126,455 10 2-3 Comp Ex 500 577.4 4.3 42.2 7.3 58 101,823 126,455 19 2-4

Table 5 provides the notched izod, heat distortion temperature andflexural modulus for Comp. Ex. 1, 3, and 4, and Ex. 2, 3, 12, and 13.

TABLE 5 Notched Izod, HDT and Flex. Modulus Notched Izod HDT @ 1.8 MPaFlex. Modulus Ex. No. 23° C. (J/m) (° C.) (MPa) Comp. 217 84 1845 Ex. 1Comp. 400 75 1400 Ex. 3 Comp. 187 73 1400 Ex. 4 2 80 103 2065 3 199 992010 12 80 103 2100 13 200 99 2000

Table 6 provides spiral flow data for Ex. 12-13 and Comp. Ex. 3.

TABLE 6 Spiral Flow Melt Barrel Temp. Temp. Ex. # (° C.) (° C.) Spiralflow @6.9 MPa, 3.2 mm mold thickness (cm) 12 227 246 — 13 227 242 17.213 238 249 22 13 249 257 27.2 Comp. Ex. 3 238 249 32 Spiral flow @ 13.8MPa, 0.8 mm mold thickness (cm) 12 227 235 5 12 238 246 5.8 12 249 2576.2 13 227 235 5.5 13 238 246 6.2 13 249 257 7.0 Comp. Ex. 3 227 235 9.2Comp. Ex. 3 238 246 10.0 Comp. Ex. 3 249 257 12.5

ESCR—Property Retention in Reverse Side Impact

Testing was conducted using injection molded flex bars with length,width, and thickness of 5.0″, 0.5″, and 0.125″, respectively. Bars wereconditioned at 23 C/50% RH for a minimum of 72 hr. Bars were clampedinto a constant strain fixture or a 3-point bend fixture at 1.5% strain,and exposed to chemical reagents using a wet patch method for lowviscosity or volatile materials, and direct wiping for high viscositymaterials. After the reagents were applied to the bars on the sidewithout ejector pin marks, the strain fixtures with bars attached weresealed in polyethylene bags for 24 hours at nominal temperature of 23 C,after which the bars were wiped clean and removed from the strainfixture.

Bars were tested at 23 C for reverse-side impact within 24-96 hoursafter removal from the strain fixture. The test apparatus was a CEASTPendulum Impact Tester equipped with a 15-Joule hammer. Bars werepositioned in a 2-inch span fixture, with the non-chemically exposedside facing the hammer. Four control bars (no strain, no chemicalexposure) were impact tested in addition to four bars that werechemically exposed. The comparison of results between the controls andthe chemically exposed bars was used to calculate percent retention oforiginal impact energy.

TABLE 7 Property Retention in Reverse Side Impact Fixture 3-Point BendConstant Strain % Retained Property - Reverse Side Impact Polymer TypePMMA PC Evonik SMMA Covestro CYRO Ineos CAP CAP CAP Makrolon AcryliteStyrolution Material Comp. Ex. 3 Ex. 12 Ex. 13 2458 H12 NAS 90 Lipids 9791 90 54 61 88 IPA 98% 80 100 91 23 0 61 Virex TB 92 100 96 0 CaviCide91 100 96 53 Sani-Cloth HB 89 93 87 65 Sani-Cloth AFIII 89 96 89 4Clorox Bleach 100 100 100 42 115 Hydrogen 94 98 94 104 peroxide CanolaOil 100 78 99 0 0 55 Windex Glass 100 100 100 27 112 Cleaner 409 Multi-91 94 92 27 39 125 Surface Cleaner SPF 30 Lotion 100 96 91 6 0 80

ESCR—Property Retention in Tensile Test

Testing was conducted using injection molded tensile bars with length,center width, and thickness of 8.5″, 0.5″, and 0.125″, respectively.Bars were conditioned at 23° C./50% RH for a minimum of 72 hr. Bars wereclamped into a constant strain fixture at 1.0% strain, and exposed tochemical reagants using a wet patch method for low viscosity or volatilematerials, and direct wiping for high viscosity materials. After thereagents were applied to the bars on the side without ejector pin marks,the strain fixtures with bars attached were sealed in polyethylene bagsfor 24 hours at nominal temperature of 23° C., after which the bars werewiped clean and removed from the strain fixture.

Bars were tested at 23° C. for tensile properties within 24-96 hoursafter removal from the strain fixture. The test apparatus was an InstronTensile Tester equipped with a 10 kN load cell. Bars were positioned inthe grips with a 4.5″ span between the grips and pulled at 0.2 in/minfor the first 0.03 inches, and at 2.0 in/min for the remainder of thepull to break. Five control bars (no strain, no chemical exposure) weretensile tested in addition to five bars that were chemically exposed.The comparison of results between the controls and the chemicallyexposed bars was used to calculate percent retention of original breakstrength and break elongation.

TABLE 8 Property Retention in Tensile Test % Retained Property - TensileStress to Break & Elongation to Break (Combined Score) Fixture: ConstantCovestro Strain Comp. Bayblend Material Ex. 3 Ex. 12 Ex. 13 T85 PolymerType CAP CAP CAP PC/ABS Formula 409 Multi-  90-100  90-100  90-100 30-40Surface Cleaner Isopropyl alcohol, 70% 40-50 80-90 80-90 70-80

Flex Creep Deflection

Injection molded flex bars with dimensions of 5″ length, 0.5″ width, and0.125″ thickness were positioned horizontally on a fixture with a 4″span, inside an oven in accordance with test set up of ASTM D2990.Weights were suspended from each bar in the center of the span, with themass selected to give a nominal 500 psi stress on the flex bar.

The bars, with weights suspended, were left exposed in the oven for thespecified duration of time. After the exposure was complete, the weightswere removed from the bars, the bars were cooled in ambient air to roomtemperature and measured for deflection of the 4-inch free span.

TABLE 9 Flex Creep Deflection Condition Reference A B Exposure Oven OvenConditions Exposure Time, hr 148 68 Temperature, C 60 90 Stress, psi 500500 Material Polymer Type Deflection, mm Ex. 12 CAP 2.2 7.0 Ex. 13 CAP2.5 9.3 Comp. Ex. 3 CAP 13.4 19.6 DuPont Zytel 101 Nylon 66 2.3 1.6Covestro Makrolon 2458 PC 0.9 0.8 Covestro Bayblend T65 PC/ABS 1.0 2.9EMS-Grivory Grilamid Nylon 2.4 5.1 TR90 BASF Luran 358N SAN 2.0 12.9Eastman Tritan TX1000 Copolyester 2.4 22.8 Evonik CYRO Acrylite H12 PMMA4.4 16.5

Dimensional Change in Moisture Test

Injection molded flex bars with dimensions of 5″ length, 0.5″ width, and0.125″ thickness were immersed in de-ionized water at 85 C for 310 hoursto achieve maximum moisture absorption. Prior to immersion, the barswere conditioned for 48 hours minimum at 23 C/50% RH.

Weight and dimensions of the bars were measured before and after waterimmersion to calculate percent change in length. An average of 3 testbars for each test was recorded.

TABLE 10 Dimensional Change in Moisture Change Weight in MaterialPolymer Type Gain, % Length, % Eastman Tenite 380-18 CAP, with PZ −0.27.8 Ex. 12 CAP, no PZ 4.0 0.9 Ex. 13 CAP, no PZ 3 0.8 DuPont Zytel 101LCrystalline nylon 8.0 1.8 DuPont Zytel 330 Amorphous nylon 4.0 1.0EMS-Grivory Grilamid TR90 Amorphous nylon 3.2 0.6 Eastman Tritan TX1001Copolyester 0.7 0.09 Covestro Makrolon 2458 PC 0.6 0.05 CovestroBayblend T65 PC/ABS 0.8 0.08 Evonik CYRO Acrylite H12 PMMA 2.2 −4.3

Examples 14-39 in Tables 11-15 were prepared as follows. The cellulosicpowder was first premixed in a drum tumbler with either KaneAce B564 MBSimpact modifier from Kaneka Corporation or KaneAce EC0100 acrylic impactmodifier from Kaneka Corporation along with 1% epoxidized octyl tallatestabilizer.

The premixed material was then compounded on a Werner & Pflerderer 30 mmtwin screw extruder at a throughput of 35 lbs/hour with screw speed of250 rpm and barrel temperature of 220° C. for the CAP 482 basedcompositions and a barrel temperature of 240° C. for the CA and CAP141-20 based compositions.

The compounded material was then injection molded into 3.2 mm thick by12.8 mm wide bars on a Toyo 110 Ton injection molding machine withbarrel temperature of 240° C. and mold temperature of 70° C.

The cellulose ester material used in the examples was selected fromEastman products CAP 482-20, CAP482-0.5, and CAP 141-20. Heat DeflectionTemperature (HDT) was determined on the molded bars according to ASTMMethod D648, as discussed above, except samples (for Examples 14-39)were conditioned by placing in a 70° C. oven for 5 hours prior to HDTtesting.

The compositions and properties of the materials for Examples 14-39 areshown in Tables 11-15.

TABLE 11 Opaque impact modified CAP materials ASTMExperiment/Composition Method Ex 14 Ex 15 Ex 16 Ex 17 Ex 18 Ex 19 Ex 20Ex 21 Ex 22 Ex 23 CAP 482-20 (wt %) 99 97 95 93 90 87 84 81 78 69 KaneAce 564 (wt %) 0 2 4 6 9 12 15 18 21 30 Epoxide octyl tallate (wt %) 1 11 1 1 1 1 1 1 1 Heat distortion temperature D648 119.7 116.4 113.3 118.3117.4 116.6 113.9 113.7 112.5 107.4 @0.455 Mpa (° C.) Heat distortiontemperature 105 100 100.3 100 95.5 96.3 95 90.2 @1.82 Mpa (° C.) IzodImpact Strength D256 79.8 181.4 183.5 201.6 201.2 201.6 202.7 181.4166.6 180 @23 C. (J/m) Izod Impact Strength 58.9 121.1 117.3 105.4588.11 80.15 101.04 115.5 95.32 @−40 C. (J/m)

TABLE 12 Clear, UV resistant impact modified CAP materials ASTMExperiment/Composition Method Ex 24 Ex 25 Ex 26 Ex 27 Ex 28 Ex 29 Ex 30Ex 31 CAP 482-20 (wt %) 97 95 93 90 87 84 81 78 Kane Ace ECO100 (wt %) 24 6 9 12 15 18 21 Epoxidized octyl tallate 1 1 1 1 1 1 1 1 (wt %) Heatdistortion temperature D648 114.6 113.5 114.1 110.9 113 110.8 107.4109.5 @0.455 Mpa (° C.) Heat distortion temperature 98.9 97.5 99.2 96.995 93.9 @1.82 Mpa (° C.) Izod Impact Strength D256 161.8 192.4 198.9216.6 215.7 230.2 199.1 180.4 @23 C. (J/m) Izod Impact Strength 105.8122.1 75.4 71.5 74.6 96.9 80 88.6 @−40 C. (J/m)

TABLE 13 High flow impact modified CAP materials ASTMExperiment/Composition Method Ex 32 Ex 33 Ex 34 Ex 35 Ex 36 CAP 482-20(wt %) 47.5 46.5 45 43.5 42 CAP 482-0.5 (wt %) 47.5 46.5 45 43.5 42 KaneAce 564 (wt %) 4 6 9 12 15 Epoxidized octyl tallate 1 1 1 1 1 (wt %)Heat distortion temperature D648 103.8 100.9 97.9 114.5 113 @0.455 Mpa(° C.) Heat distortion temperature 96.2 @1.82 Mpa (° C.) Izod ImpactStrength D256 163.8 161 145.4 141.6 179.7 @23 C. (J/m) Izod ImpactStrength 97 100.8 122.5 122.6 85.5 @−40 C. (J/m)

TABLE 14 High temperature impact modified CAP material ASTMExperiment/Composition Method Ex 37 Ex 38 CAP141-20 (wt %) 99 84 KaneAce ECO100 (wt %) 0 15 Epoxidized octyl tallate (wt %) 1 1 Heatdistortion temperature D648 148.6 147.7 @0.455 Mpa, (° C.) Heatdistortion temperature @1.82 Mpa, 128.4 126.8 (° C.) Izod ImpactStrength @23 C (J/m) D256 45.5 85.0 Izod Impact Strength @−40 C (J/m)35.7 45.8

TABLE 15 CAP blended with a modified olefin impact modifier ASTMExperiment/Composition Method Ex 39 CAP 482-20 (wt %) 84 Lotader AX8900(wt %) 15 Epoxidized octyl tallate (wt %) 1 Heat distortion temperature@0.455 Mpa, (° C.) D648 97.2 Heat distortion temperature @1.82 Mpa, (°C.) 115.1 Izod Impact Strength @23 C, (J/m) D256 117 Izod ImpactStrength @−40 C, (J/m)A review of Tables 11-15, show that examples 15-36 and 38-39 have highertoughness than examples 14 and 37, that do not contain impact modifier.

Melt Processibility of Example 26

The flow behavior of Example 26 from Table 12 above was compared totypical plastic material using a spiral flow test. The spiral flow testwas conducted filing a 0.5″ wide×0.125″ thick spiral flow mold withmolten material using a Toyo 110 ton machine with an injection pressureof 1000 psi, injection speed of 1.0″ per second, fill time of 10 second,screw speed of 150 rpm, back pressure of 100 psi, cooling time of 22seconds. The flow length is the length of the spiral of each materialmolded at a specific barrel temperature under the same moldingconditions.

Spiral Flow was first run to determine the flow length values of certainpolymeric materials. The materials used were Makrolon 2458 polycarbonate(PC) from Covestro, Lustran SAN 31 (styrene-acrylonitrile or SAN) fromINEOS, and Terluran GP22NR ABS from INEOS. These materials were run atprocessing temperatures, as shown in table 16 below.

In addition to the materials discussed above, spiral flow was determinedfor example 26 and comparative example 3. These materials were run atprocessing temperatures, as shown in table 16.

TABLE 16 Spiral Flow Length Spiral Flow Material Barrel Set Point ° F./°C. Avg. Fill (inches) ABS 460/238 21.75 ABS 480/249 25 ABS 500/260 28.75SAN 420/216 15 SAN 440/227 18.75 SAN 460/238 22.25 SAN 480/249 25.75 PC500/260 7 PC 520/271 10.5 PC 540/282 13.75 PC 560/293 17 Ex 26 480/24927.25 Ex 26 460/238 22 Ex 26 440/227 17.25 Comp. Ex 3 400/204 25 Comp.Ex 3 420/216 32 Comp. Ex 3 440/227 38

A review of table 16 reveals that the flow length values of thecommercial materials is between 10 and 30 inches. The spiral flow ofexample 26 shows that the composition has very good flow (similar to ABSand SAN and better than PC) indicating that the examples of theinvention can be melt processed in injection molding and otherprocesses. The spiral flow length of comparative example 3 (fullyplasticized CAP with no impact modifier) was the highest.

In examples 40-44, cellulose ester compositions were prepared bycompounding CAP 482-20 with additional impact modifiers, includingseveral block copolymer thermoplastic elastomers, and an ABS core-shellimpact modifier. The compounding of the cellulose ester compositions wasconducted on a Leistritz 18 mm (50:1 L/D ratio) twin screw extruder at athroughput of 18 lbs/hour with screw speed of 250 rpm and barreltemperature of 220° C. The barrel temperatures were 230° C. forcompounding CA and CAP141-20 based compositions. The compounded materialwas then injection molded into 3.2 mm thick by 12.8 mm wide bars on aToyo 110 Ton injection molding machine with barrel temperature of 240 Cand mold temperature of 70 C. Properties for these compositions arecompared to example 14 in Table 17.

Glass transition temperature (Tg) was measured according to ASTMStandard Method D3418, where the sample is heated from −100° C. at aheating rate of 20° C./min. DSC scans of blends of materials may showmultiple Tg transitions. If more than one Tg transition was determinedduring the scan, the matrix glass transition is defined as the highestTg measured during the scan.

Notched Izod Impact Strength was performed on 3.2 mm thick molded barsat 230 C after notching according to ASTM Method D256, afterconditioning the bars at 230 C and 50% RH for 48 hours.

TABLE 17 CAP blended with selected block copolymer impact modifiers oran ABS core shell impact modifier Experiment/Composition Ex 14 Ex 40 Ex41 Ex 42 Ex 43 EX44 CAP141-20 (wt %) 100 90 90 90 90 70 Blendex 338 ABScore shell impact 10 30 modifier (wt %) Kraton FG1924 G SEBS block 10copolymer (wt %) Estane ALR 72A TPU block copolymer 10 (wt %) Hytrel3078 polyester-ether block 10 copolymer (wt %) Glass TransitionTemperature (Tg) 147 142 142 142 141 139 Izod Impact Strength @23° C.(J/m) 79.8 210 379 316 219 226

Other embodiments will be apparent to those skilled in the art fromconsideration of the specification and practice of the embodimentsdisclosed herein. It will be understood that variations andmodifications can be effected within the spirit and scope of thedisclosed embodiments. It is further intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the disclosed embodiments being indicated by the following claims.

That which is claimed is:
 1. An injection molded article comprising athin-walled body portion formed from a polymer-based resin derived fromcellulose, wherein the thin-walled body portion comprises: i. a gateposition; ii. a last fill position; iii. a flow length to wall thicknessratio greater than or equal to 100, wherein the flow length is measuredfrom the gate position to the last fill position; and iv. a wallthickness less than or equal to about 2 mm; and wherein thepolymer-based resin is a cellulose ester composition that comprises animpact modifier in an amount from 1 to 30 wt % and a plasticizer in anamount from 0 to 10 wt %, based on the weight of the cellulose estercomposition, and wherein the polymer-based resin has an HDT or at least95° C., a bio-derived content of at least 20 wt %, and a spiral flowlength of at least 3.0 cm, when the polymer-based resin is molded with aspiral flow mold with the conditions of a barrel temperature of 238° C.,a melt temperature of 246° C., a molding pressure of 13.8 MPa, a moldthickness of 0.8 mm, and a mold width of 12.7 mm.
 2. The injectionmolded article according to claim 1, wherein the flow length to wallthickness ratio is in the range from 250 to
 1500. 3. The injectionmolded article according to claim 2, wherein the flow length to wallthickness ratio is in the range from 500 to
 1500. 4. The injectionmolded article according to claim 1, wherein the wall thickness is inthe range from 0.1 to 1.5 mm.
 5. The injection molded article accordingto claim 4, wherein the wall thickness is in the range from 0.1 to 1.0mm.
 6. The injection molded article according to claim 5, wherein thewall thickness is in the range from 0.1 to 0.5 mm.
 7. The injectionmolded article according to claim 1, wherein the polymer-based resin hasan HDT in the range from 100° C. to 140° C.
 8. The injection moldedarticle according to claim 1, wherein the polymer-based resin has abio-derived content in the range from 40 wt % to 60 wt %.
 9. Theinjection molded article according to claim 1, wherein the polymer-basedresin has a spiral flow length of at least 5.0 cm.
 10. The injectionmolded article according to claim 1, wherein the polymer-based resinfurther comprises at least one property chosen from: flexural modulus ofgreater than 1900 MPa as measured according to ASTM D790 using a 3.2 mmthick bar hat has been subjected to 50% relative humidity for 48 hoursat 23° C.; a notched izod impact strength of greater than 80 J/m asmeasured according to ASTM D256 using a 3.2 mm thick bar hat has beensubjected to 50% relative humidity for 48 hours at 23° C.; a flex creepdeflection of less than 12 mm, measured using a molded bar havingdimensions of 5″ length, 0.5″ width, and 0.125″ thickness positionedhorizontally on a fixture with a 4″ span, inside a dry oven for 68 hoursat 90° C. with a nominal 500 psi stress on the center of the span; atransmission of at least 70 measured according to ASTM D1003 using a 3.2mm plaque after injection molding at a barrel set point of 249° C. and aresidence time of 5 min; a ΔE value of less than 25, using a 3.2 mmplaque after injection molding with a barrel temperature of 249° C. anda residence time of 5 min; or an L* color of at least 85, measuredaccording to ASTM E1348 using a 3.2 mm plaque after injection moldingwith a barrel temperature of 249° C. and a residence time of 5 min. 11.The injection molded article according to any of claim 10, wherein thepolymer-based resin comprises at least 2 of the listed properties. 12.The injection molded article according to claim 1, wherein thepolymer-based resin contains no plasticizer.
 13. The injection moldedarticle according to claim 1, wherein the gate position comprises a gatehaving a gate size, wherein ratio of gate size to wall thickness 0.5:1or less.
 14. The injection molded article according to claim 13, whereinthe gate size is in the range from 0.1 to 0.5 mm.
 15. The injectionmolded article according to claim 14, wherein the wall thickness is inthe range from 0.2 to 1.0 mm or less.
 16. The injection molded articleaccording to claim 1, wherein the polymer-based resin comprises acellulose ester chosen from cellulose acetate propionate (CAP),cellulose acetate (CA), or combinations thereof.
 17. The injectionmolded article according to claim 16, wherein the cellulose ester is CAPand the polymer-based resin comprises 0-1 wt % plasticizer.
 18. Theinjection molded article according to claim 17, wherein thepolymer-based resin comprises CAP and contains no plasticizer.
 19. Theinjection molded article according to claim 16, wherein the celluloseester is CA and the polymer-based resin comprises 1-10 wt % plasticizer.20. The injection molded article according to claim 19, wherein thepolymer-based resin comprises CA and contains plasticizer in an amountfrom 1 to less than 10 wt %.